CA1048188A - Self-stripping coating composition - Google Patents
Self-stripping coating compositionInfo
- Publication number
- CA1048188A CA1048188A CA229,046A CA229046A CA1048188A CA 1048188 A CA1048188 A CA 1048188A CA 229046 A CA229046 A CA 229046A CA 1048188 A CA1048188 A CA 1048188A
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- CA
- Canada
- Prior art keywords
- composition
- resin
- acid
- monomer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/06—Other polishing compositions
- C09G1/08—Other polishing compositions based on wax
- C09G1/10—Other polishing compositions based on wax based on mixtures of wax and natural or synthetic resin
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE: An improved stable self-stripping aqueous coating composition, adapted to simultaneously disperse a previously desposited dried coating composition and replace the dried composition with a fresh coat, includes a solution of a alkali soluble resin of low molecular weight and high acid number and aqueous ammonia in sufficient concentration to provide a pH no less than about 9Ø Surfactants and waxes may also be employed in the coating composition as well as conventional additives, however, metal-fugitive ligand complexes are not needed for the self-stripping properties.
Description
~8~
BP~CK~ROUND O~ THE I~nrENTloN
.
The pre~ent lnvention xelate~ to stable, aqueous coating compositions. In partl~ular 1:he lnventiorl relate~ to ~n lmpro~red 8tZl~le aquaou~ coat~ ng compo~lt~on containing a~ the prim~ry coatfng agent an alkali ~oluble rl38ill oiE low molecular weight and high ac~d num~er and aqu~ou~ ~rmnonia ~uific~ent to proYide a p~l no le~ than about 9 . 0 .
In the protective coating ~ield, such a~ temporary oxganic coating~, including certain f loor coating~ J ~ t ~ des~rable to haYe m~ n~mum carboxyl ~unctionality pr~en~ in oxder to avoid h~ ~olubili~ing and ~potting efîec~s nor~ally obtalsed wh~n water ~8 brought into contact with su~h coating. t~owever, the hardnes~, durability, gloss, and removability propertie~ o~ th~se ~llms are ~ffec~ed by th~ degr~e of carboxyl functionaliSy present. There-~vreJ mo~t coating compo~ on~ de~eloped here~o~or~, represen~ a compromise with re~pect to prope~tles ~u~h a~ hardne~, duxability, ~10~5, removal~ility, and xe~istanceO
~: It ha~ been found th~t YariOU~ organ:5c fllm~ contalnin~
carboxyl functional~ty suffici~nt to obtaln ~s~sy removal, tend, - upon aging, to und~rgo a degrading e~fect; that i8 a 10~8 0~
functionality which xender3 th~ carboxyl ~roup~ ~ubstantially `
unavallable. Thi~ degra~ln~ ect produce~ 1~ms wllich are dl~ficult to ren~o~re by means o~ conventional film remov~r sub-stance~, such as de~ergents, and re~ult~ in ~llm bulldup. Film buildup is usually accompanied by degrada~ion. in color9 for example~
y~2110wing, and ev~ntually necessita~es complet& ~ilm removal w~th hi~h caustlc ~olutlons or 80'l ~tions containing organic solventEI or by variou~ abrasive method~, all o which have been found to e~ect the sub~trate ~dversely.
The problelD of removability, degradat~on and fllm bu~ld-up was alleviated greatly by the u~ o~ the mi~t~l crosR-linked , :`~
polym~r~ di~clos~d in ~.S. Patent~ 3,308,a78 and 3,320,1~6.
The metal ~omplex salts d~sclo~ed in the above patent~ ~orm tempoxary bond~ or cro~s-link~ b~tween ad~acent polymer carboxyl funct~onal group~ ~o aB to retard their exposur~ and sub~equent degradat~on.
These 1vor coating composi~ion~ provided fllms w~th good glosa and strength which could be e~sily removed by cleaning with d~ter-gent and ammonia but are water in6ensit~ve and detergent resls~ant under no~mal co~di~ions.
For many applications, among them the ho~, it has been deemed desixahle to malntain hl~hly poli~hed ~loox ~urfaces fQr ae3th~tic appeal as well as ~or other rea~on~. In lleu of detergent-cleaning a y~llowed or d~rty floor f~lm, it i~ ~onsidered hiqhly de~irabla to merely recoat and thereby ~lmultaneou~ly clean and remove the old polish layer and onm a new ~il~. Accor~-ingly, the ~eed has arisen for a ~elf-str$pping ~loor polish adapted to be frequently reapplled to main~ain a hi~hly polished ~ub~tratc which i8 not to be wa~hed with detergen~ between appllca-tions. The polish must have non-yellow~nq ch~racteri~tlcs and be ~hel~-stabl~O
Re~er~tly, various innovatlons have been ~ntroduced permitting a drled floor coat~ng to be ~imultaneou31y cle~ned and polished without th~ need for conventlonal washing and repol~
~3hing, and withou~ f~lm buildup. As illustrated in U.S. Patent 3,308,0~8 ~odiications in the ab~a type o~ f~rmulation can prvduce a st~ble, aqueou~ coating compo~itlon whlch provide metal-contsining organic fiLm~ having unique ~tructural int~grity;
captive functional groups which are not easily degraaed; controll~d removability and high ylo~s, hardne~s and durab~lity. These coatings are designated as sel-~en~itlve coating~ and after appl~cation ~re resistant to detergent washlng and can ~e re~o~Qd hy recoating. Upon recoat~ng, a portion of the dried ~ilm i8 ;~
~9L8~L~8 -.; dlspersed i~ the f resh coat~ ng and a n~w coating i5 provid~d whLch is substantially ~ree ~rom the heel mark~, scuffs, and oth~r dirt contained ~n the old dried coatlng.
:
The ~table sel~-~tripping aqueou~ flovr ~oatin~ co~po-s~tion of the presen~ invent~ on co~prlses ~s ~he pr~mary coating agen~ a solut~on of an al~al~ ~oluble resin having a weigh~ av~r~ye molecular welght of front about 500 to about 4~,OOO and an ac~d number withln the range of from 120 ~o ~50. ~hi~ al~ali soluble re~ln is an addition res~n conta~n~n~ at lea~t two ethylenically unsaturated monomers, one of ~hese monomers be~ng a ligand-free mononter while the other monomer contains carboxyl functlonal group~. The coating c~mpos~tion o~ thQ pre~ent inventlon also include~ aqueou~ ~monia in a concentra~lon ~uficient to provide a pH o~ no less than about 9.O and a com~ined amount of wax, olvent, level~ng agent, surfaatant and hlgh molecul~x weight polymer equal to or greatar than 9~ ~y wei~ht of the r~sin.
Thi~ co~position i5 raadlly adapted to dispers~ a previously depo~ited dried coating compo$it~on of lt~el~ and replace th~
dr~ed coating with a fresh aoatlng having even glo~ ~nd durability.
.
SU,~RY OF T~E INV~NTION
~ t i8, therefore, a primary ob~ect o~ the pxe~ent lnven-tion to pro~ide an ~mpro~ed ~el~ ripping coating compo~ition.
It ~8 ~ ~urther ob~ect of the invention to pxovide a sel~t~ipping coating compo~ition fxee from the tendcncy to gel and change visc03ity upon storageO
It i~ a further ob~ect o~ tho pre~ent invention to pro-vide a ~imple ef~icient ~elf-~tripping composition which doe~ not contain any metal complexing agent.
It i~ another ob~ct of the invention to provide a coating composition sdapted to remove deep scuff~ and scratche~ fror.
previo~ly poltshed floors upon recoating.
`:
L
~48~
It is an addltional ob~ect to provlde a ~elf-~3trlpping coating compos~tisrl adapted ~o dlsper~e a previously applied coatlng ~nd to recoat a sub~trat~ wi~h ~ub~ntlally a slngle layer of n~3w coa~ing ~ilm, thereby reducing 02 elimlna~ing 'che bulldup ~n ~ilm thic3cne~ that characteri~e~ conYentional ~loor pollsh~s.
St~ 11 fur~her ob~ects and advantages o~ the floor poliF~h compo~ition of th~ present inven~ion w~ 11 become more apparent Prom the following more detailed descriptt on th~x~o~ .
DE~INITI()N5 ~ or the purpo~e~ of the pre~ent invenl-ion a "stable"
corRpo~ltlon i~ defined a~ ~ fluid substance which can be storQd ~or prolonged periods and i~ subs~anti~lly free from gelling and substantially free from changes ln viscos$ty. It i~ e~serl~ial tha~ the ~el~-stripping coating compo~itton~ of the inven'c~on be ~t~ble~ In ord~r to obtain the ~elf-strippi~g ilms of ~h~
~nv~3ntion a~d in oxder ~o dl~per~e a ~ubs~antial amount o~ the film, th~3 self-~trippiz~g coating c:ompo~ tion mu~t b~ ~ub~tantl~lly fxee fro~n gellation and/or precip~ation and hav~3 substan~lally ~be sam~ composltior~ throu~hout.
, . . . . .
The ~tab~l;lty of the presently claimed ~elf ~tripping coat~ ng composit~ ons can be monitor~d hy per~ odic optical den~ity ~easurem~nts and can be verlfled by monitorillg phy~ al change~
i n the compo~ltions durln~ prolonge~ cc)ntinuous exposur~ At high temperature c:ondit~on~. Procedure~ for monttorln~ optical dan~ity and phy~ical cha~qes are ~llustrated ln U.S. i,308,0780 ~ 8 employed h~r~n, the te~ H~elf-str~pping" r~2r~ to thæ a~llity o~ the in tant coat~ ng composition~ to react with a f~m obtained from the c~;nposi tlon and to disper~e a -~ubstantial quantity o~ tha film ~n the liquld coating composition in les~
than half a mirlute. Alhs~, the term "~multan~ously", when used _5_ L
8~8 to describ~ a "sel~-stripping" compositiorA, mean~ the compo~l~ion di~per~e~ in les~ than hal~ a ~l~ute.
As employad hereln, the "acid n~r" o~ the r83in8 used ln the pre~ent inventiorl 18 th~ actual ox obsex~ed valu~ a~ di~-tlngu~ shed ~rom th~ th~oret~cal value and can be ob~erved by dls-~olving the xesin ~n a solutlon conta~ning 66g~ by weigh ethanol and 34~ by weight ben2ene and titrating th~ resin/solvent mixture to the phenophthalein end polnt with a 0 01 W a~ueous ~0~l 601utionO
~ha~ gener~l procedure i~ described by Pinner in "Pract~ ~1 Cour~e in Polymer Chemistry" ~1961), F~rgamon Pxess, ~ew York, New York, at page 113. ~t ls understood ~or ~h~ purposes o~ ~he pre~ent in-r~ntion that the ten~ "acid ~alue" can l~e u~ad inter~:hang~ably w~Lth the torm "ac~d m;mber".
DEq~AILED DESCRIPq~TON O:l? T~E ~ NTION
The pre~ent iAvention i.~ dir~cted to a ~table coatlng compo~i~ion adap~ced to ~im~ltaneou~ly dl~per~e a pre~ou~ly deposited dried coat~ ng r:ompo~ition and replace the drl~d compo -8ition with d iEre3h coating comprising 50-96% by we~gh~ watsr, 0-1096 by welght pla~tlcizer, 0~ by weight l~veling agent, 0- la~6 by we~ght or~anic 301vent, 0-5% by weight ~ur~actant" 0-15~6 by weight wax, 0-10~ by wei~ht ~ilrn-rnodifying pol~ner and 3-18P~ by weight polymer.Lc coating agen~, with th~ pro~ 8C~ that the total non-volatiles of the compo~tion 13 ~n the rang~ o ~rom 4-20~
by weighlt, a:nd ~he com~ined non~volatlles of the leveling agent, solvQnt, p~ticizer, surfactant, wax and f~ lm~modi~yin~ polymer ar~ equal to or greater than 9% of the non-vc3atile~ of the polymer~ c coat$ng agent wherein the lmproveTnent co~prise~ u~n~
a~ the pol~;leric coatinS~ agent a 801ut~0n of an allcali soluble x~ln having a we~ght average molecular weight from about 500 to ~$0, 000 and an acid number ~rom about 120 to 550, sa~d resin baing an addition resln ~ormed frc~m ta) at lea~t 1 ethylen~cally ~` ~
1318~
un~aturateà ligand-free ~nonomer and (b) at laast 1 ethylenlcally un~aturated mono~ner h~ring at lea~t 1 carboxyl group, whsrein sald resins contain from abou1: 40-8~ by welght of monomer (a) and ~rom 60-lS'g by weight monomer ~b~, adding a~ueous a~nnonia to ~aid composition in an amo~mt sufficient to provlde a pE~ of no le~s than 9. 0, and said composi~on belng sub~antially ~ree o~ complex salt~ oî cro~3-linking metals ~uch a~ zinc, cadimum, copper ~ etc ~ he pre~erred 8elf strippi~g 5tab~e coating compo~itions of the present invention ars aqueous compositlon~ cc: ntaining pre~erably from about 4~ to about 18% rlon-~rolatiles . Particularly enhanc~d g~loæs and ~elf-stripping characterist~c~ are obtain~d when the aqueous cornposltion contain~ ~rom about 10 to 14~ non-volatiles by weight.
In addition to the abo~e ~e~f ~tripping stal~le coating compo~ ion~ containing from about 4~ to 20% non-~rolatlles, the composition of ~he present in~rent~on may also be p~repared in a concentrated or bucket-dilutable ~orm containing up to about 55~ ~olid~. O;E course, these concentrated cornpo~ition~ are de~lgned to be diluted during use to a composition havin~ a solids cont~nt batween 4% and 20B. Alternativelyt the concentrated product may be airectly appl~ed to the ~loor and subsequently ~opped or diluted with a wet mop.
Th~ ~ucket-dilutable ~ompositio~ o~ th~ present inventlon util~ze the same materials in the same re~ative ratio~
The only di~:eQrence i~ that the ~olids level is greatly incxeased whlle the water level ~ reduced. These composltions co~prise 20-50~ by weight water, 0-20~ by w~ght plastici~er, 0-10~ by weight leveling agent, 0-25~ by we~ght organlc solvent, 0-20~ by we~ght sur~actant, 0-20~ by weight wax, 0-20~ by weight ~il~
modi~ying polymer and 18-45~ by weight poly~eric coat~ng a~ent at a sol~d~ level o ~rom 20 55~.
~ he resin~ ~or u~e R~ th~ polymeric coatlng agent ~hould be alkali soluble and contain at least about 0.0021 e~uivalent of carboxyl ~ro~p~ per gram of res~n and be ~apabl~ o~ being substantially compIet~ly ~olubilized when a minim~m of ~rom about 80 to 90~ o~ these carboxyl groups ar~ neutralized with an aqueou~
801utlon of ba~ic substances ~uch as borax, a~ines, ammonlum hy~rox~de, sodium hydroxide and/or pota~sium hydrox~d~. ~or example, a ~uitable styrene~acrylic acid xesin ha~ing ~n acld number o~ about 190 would contain no le58 than about 0.0034 equiva-lent o~ carbo~yl groups per gram o~ resin and w~uld be ~u~tantially completely solubillzed when a mi~imum of ~rom about 80 to 90~
~f the caxboxyl ~roups are neutralized by an aqueou~ base solutlon.
The alkal~ soluble re~ins u3eful ln th~ composition ¦of the present invention axe addition re~in~ co~tainin~ at lea~t two ethylenically unsatura~ed monomers. One of these said monomers should be a hard monomer, sometlme~ referred to as the ligand-~rea mo~omer. The o~her monome~ should be a ligand-conta~nlng polymerizable monomer providin~ the necessary acid ~untlonality which contribute~ substantially to filM per~vrmance and ~s~i8t8 in ~aintaining ~uch des~rable propertie~ a~ film hardne~s, glos~, durability and controlled removability.
The acid number o~ the low~r molecular we~ght alkali 901~ble xe~i.ns i5 critlcal and influences both the ~olub~lity o~ the xe~ins in the aqueou~ al~aline coatin~ compo~itions and al80 th~ sel~-xtrlppin~ properties o~ the film~ produced ~ro~
the~e compo~itions . For example ~ at an acid number substanti~lly b~low about 120, certain of the add~tion res~ns are rela~ively in~olubl~ in the aqueous coat~ng cvmpo~itions o~ the inve~tion.
Al~o, at the~e low acid n~ber~, the films ~ormed from such resin5 are not readily self-~trippa~le and deter~en~ and the like mu~t be ~mployed with high alkali content to remove films ~oxm~d from 8~
~uch re~ ns. When the acid number o~ the addition resln i~ substan-ti~lly above a~out 550, th~ ~ilms ~orme~ from such coatlng cotnpo8~-tion3 tend to be high~y sub~eo~ to wa~er spotting. Accordingly, for the fiel~ s ripping coatlng ~o~posltion~ the acid value oiE
th~ addition resin ranges betwe~n 120 and 550, between abc:ut 150 and 300, and most pre~erably will ran~e ~xom about 150 to a~out 250.
~ he molecular weight o~ ~he alkali xoluble resin~ of the invention 15 also critical. The generally low molecular weight of the p~eerred polymers keeps the viscosity o~ the coating compos~tion w~thin acceptable limit~. ~he ViBCo8ity of a ~olution of the alkali ~oluble polymexs is stron~ly dependent on the pH, on the aci~ n~ber, a~d on the molecular weight o~ the res~n~.
~8 stated hereinaboYe~ it is necessary to keep the pH o~ the coating composition at a relatively high level~ Ther~fore, to control vlscosity and to ~ ncrease the ~esin ~elf-strippins ~ it ha~ been ~ound tha low molecular weight polymer~ are necee~ary.
The preferred molecular welght for a speciic al~cali ~oluble re~in is, in p~rt, dl~tated ~y its aaia nu.~er, the p~
o~ the coating composition employing the resin and the percentage o~ ~olids in the coating compo~ition . To assist ~ n the disper~ion of the dried film upon recoating, to control ~rlsco~ity at ~ low level and to enhance the glo~ of the pre~erred coating compo~itions, re~ns having a w~ight average molecular weight ~rorr about 500 to 40,00D ~hould be used, wlth polymex~ having a molecular we:lght o~ 500 'co 30, 000 being preerred and those w~th a molecular we~ght s>~ 500 to lO,OOO ~eing mo~t preferred slnce enhanced result~
are obtained.
For the purpo~e~ of the pres~nt invention, the ligand-~ree r.lonomer should be free from any atom~ mol~cule, or lon capable of ~or~3ing a coordlnate bond, such as a carhoxyl ion . Suitahle ligan~ ree monomer~ must also be c~pa~le of undergolng additlon -.
` `` 3l~48~L138 ~ polymerization. The resins should contain from 40 to 85%
.- ligand-free monomer and preferably 40 to 75%.
If desired, the ligand-free monomer can be a mixture of monomers. Exemplary of such ligand-free monomers ~ are vinyl toluene, methyl methacrylate, butyl methacrylate, --~ acrylonitrile, vinyl acetate, styrene, 6~ -methyl styrene, .. .
butyl acrylate, ethacrylate, 2--ethylhexyl acrylate and mixtures. Other suitable monomers and comonomers are disclosed in U.S. Patent 3,308,078, columns 9 and 10.
~;j 10 The ligand-containing polymerizable, ethylenically unsaturated monomer utilizes carboxyl groups as the prefer-red polymer ligand. Preferred ligands are ethylenically unsaturated alkanoic and alkandioic acids, particularly those having 3 to 8 carbon atoms. Examples of preferred acids include acrylic, methacrylic, crotonic, isocrotonic, maleic, fumaric, itaconic acids and anhydrides of these acids, as well as mixtures thereof.
;, '. ! , Stability and self-stripping of the coating compositions are enhanced; and, accordingly, it is ~
;~; 20 preferred to employ an alkali soluble resin containing ~!' acrylic acid, methacrylic acid, or mixtures as the ~- ligand-containing monomer.
In general, the minimum weight percentage of , . . .
ligand-containing monomer in the alkali soluble resin will be determined by the amount of acid functionally necessary to give the resin required alkali solubility in aqueous media. E'or most purposes at least about 15%
and preferably 25% by weight of resin of ligand containing monomer is employed. The maximum weight percentage of ligand-containing monomer is determined by a combination of various factors; among them viscosity of the resulting composition, water spotting sensitivity of the dried coat ::-- ~ -10-.. :, . ~ ' ' ', .
: . , , . resulting from the coating composition and tackiness of .: the resulting film when the coating composition is : applied to a subtrate.
,~
, ,.
-lOa-10481~ 1 In gQneral up to a~ou~ 60% by wel~h~ l~gand-containing mOnomQr may be employed ~n the re~in. A~ove about 60% monomer ; the r~ultlng coating composlkion t~nd~ to become exce~ively .- vi5cou3 dur~ng storage and during use- Furthar, the dried ~
-~i re~ulting whQn the coating compo~ition contalning the mono~er :
` i8 applied is excesslvely watex sensitive and will have a tendency :
to ~pot unduly.
Al~hough any combination o~ the above monomers ~ the ranges set orth above which ~orm~ a continuous ~ilm will be suitable for use ~n the sel~-~tripping f~nish of the present invent~on, resins ~ade from the followin~ co~bination~ of monomer~
are preferre~: styrene/acrylic acid; styrenefmaleic anhydride;
methylmethacrylate/butyl acrylate~methacrylic acid; ~-methyl-styrene/ethyl acxylatefacrylic acid; 3tyrene/~utyl acrylate/acrylic acids and styrene~methyl methacrylate/butyl acrylate~methacrylic acid.
A pre~erred alkali solublQ resi~ i~ a 68% styren~/32 acrylic acid re~in having a wQight avera~e molecular weight of about 500 to 10,000. Other pre~erre~ addition r~in~ include a partially Qsteriied ~tyrene-maleic anhydri~e resin hav~ng a~ acid numhex o~ about 200 and a molecular w~iqht of about 1400 and a 45% ~-methyl~tyrene/3C% ethyl acrylate/25% acrylic acid having an ac$d nu~.~er of lS5 and a weight averaye molecular weight o~ 5,000. In general, styrene-acrylic acid resins havin~ number averag~ molacular weight~ ~rom about 2,500 to 4~500 and weight av~raye molecular welght~ o~ 6,500 to 9,500, a~ well a~ an acid number of 170 to 200, are particular preferred.
~ queous amm~nla i~ present in the coatlng composl~i~ns o~ the inventlon in a concentration su~ic$ent to pxovide a pH
of a~ least about g.0 and preferably above ~.S. It ha~ been found ~hat th~ hicJh p~ level subst~t~ally cnhances the 5~1-s~ripp~ng character o~ th~ compo~ition. Amm~n~ may be providcd in the coatlng compo~ition in the form o~ concentrated ~monium hydroxide. A portion or all o~ the ammon~m hydroxlde may be r~placed wlth sodium or potas~lum hydroxide or organia aminQ.
I;ow~ver, such r~placement is u~ually accompanied by a decrease ~n th~ water resist~nce (spotting resistancQ) o the product.
i In order to enhance the characteristics of a Pilm ~ormed `; ~rom the instant coatin~ compo~ition from 0-10~ by weight o~
:.................................... .
::- - a polyhydroxy polyether~ a lower alkanol or h~gh-~olling ~lycol , '~ i3 pre~ent in the present composition~ These organic solvents aid in extending the drying tlme of the coat~ny composltion and impart~ increased gloss and 1QV~1ing characteri~tics to the comp~-si~on. Typ~cal polyethers ~nclud~ mono- and di-alkyl ethers -~ o~ diethylene glycol and their derivatlves, also ~nown as car~itol~O
:- Typical glycols are e~hylene glycol, polyethylen~ ylycol, propylene glycol~ polypropylene glycol, etc~, while the alkan~ls inc~ude - i~opropanol, hutanol, etc. ~ p~rticularly preferred polye~her , .
is d~ethylene glycol monoethyl ether. mh~ polyethers can be used alone or combin~d with the alkanol~ or polyhydr~c alcohol~, such as ethylena ~lycol.
The film fonming c~mpositlons ~ay contain from about O
to 10~ by weight plastici~ers wherever nece~sary, to provide a of suitable h~rdne~s and appearance. It has been ~ound ~ha~
most hard ~e.sins can be pla~ticized to improve their ~llm ~ormin~
properties. Since the purpose of the pla~ticiz~r ls to impart ~lm osming properties to the coatin~ col~position ana since it 18 not always necessaxy to impart flexibillty to the resin composttion wllen it is inherently tou~h and fle~lble, a ~ug~tive or ~e~i-fugitive plasticizer may ~ometimes be employed rathar th~n a permanent plasticizer. ~iixtures of fugi~ive and permanent pla~ti~izers may also be employed.
~ xamples of essen~ially permanent plasticizers that ar~
~uitable lnclude benzyl butyl phthalate, ~ibutyl phtha~ate, . _~ L,.
1~818~3 dimethyl phthalate, triphenyl phosphate, 2-ethyl hexyl benzyl phthalate, butyl cyclohexyl phthalate, mixed benzoic acid and fatty oil acid esters of pentaerythritol, poly (propylene adipate) dibenzoate die~hylene glycol dibenzoate, tetrabutylthiodl-succinate, butyl phthaly butyl glycolate, triethyl citrate, acetyl trlethyl citrate, tributyl citrate, acetyl tributyl citrate, dibenzyl sebacate, tricresyl phosphate, toluene ethyl sul~onamide, the di-2-ethylhexyl ester of hexamethylene glycol diphthalate, di-~methylcyclohexyl)-phthalate and tributyl phosphate.
Exampl,es of fugitive plastici2ers include the monethyl or monomethyl ether of diethylene glycol, isophorone, benzyl alcoh~l, and 3-methoxybutanol-1. The particular plasticizer amount thereof employed are chosen in accordance with the demand for c~mpat~b~lity and efficiency by making the fi~m more flex1ble.
A particularly preferred pla~iaizer which al50 serves a~ a leveling ag~nt is tributoxy,ethyl phosphate.
An extremely desirable ingredient in the present coating compositions which serves as a leveling agent and a self-sensitiæer of the composition is a sur~actant. I~ is preferred to employ anionic or nonionic sur~actants and part~cularly non-~oaming surfactants to reduce the tendency of the coatlng composition to form bubbles upon application. The sur~acta~ts increase the storage stability o~ the composi~ion and permit even film formation of the coating composition upon application (leveling).
Usable water soluble, low foaming'nonionic surfactants include organo-ethylene oxide condensates as described in U.S.
Patent 3~308,078, in columns 21 and 22.
' , Example~ o~ suitable low foaming anionic sur~actants in~lude alkali metal and ammonium salts of higher ~atty acids havlng 12 to 22 carbon atoms. Typical anionic surfactants include the sodium, potass~um, ammonium and morpholine oleates, ricin-oleate~, ~tearates or i30stearates.
1~48~B8 .~' Mixtures o~ an~onlc and nonlonic sur~actants may be : employed. Enhanced result~ are obta~ned; and, accordingly, lt is ; preferred to employ a ~xture o~ olQiC acid and octylpheno~y ~` polyethoxy ethanol as surfactants.
~; Th~ uantlty of sur~ac:tant~ employed will depend in part upon the character~ st~ C8 of the al~ali soluble resin . In general ~: from about O to 5~ by weight surfactants are employed based on the weight of the total co,~pos~t~on.
I~ desired, the pre~erred plastici~er and surfac~ants , , .
can be replaced in part with dibutylphthalate; however~ the glo~s and leveling characterist~cs o~ the resulting films are impalred s~mewhat.
In addition to the sur~actants and plasticizers, alkaline bullders such a~ the ammonium and alkal~ metal salts of ethylenedi-am~na tetraacetic acid, nitr~lotriacetic acidf diethylenetriami~e- ::
pentaacetic acid, citrio acid, and the phosphonates can be opt~on-ally included to pro~ide 3tab~1ity and improved cleaning character- ~-~stic~ 3n an amount o~ from O to 5~ and pre~erably 0 to 2~.
In addition to the levelin~ ~unction of some pla~t1cizers and surfactant~, the compos~tion o~ the presen~ ~nYention al80 may inc:lude from O to 5% o a leveling agent to assi~'c the cor~po-sltion ~n level~ny over other finishe~ such as the fluorochen~cal leveling agents disclosed in U. S. 2,937,098, gelatine, perfluorinated cyclo-compounds disclosed in U. S. 3,163,547, and other known leveling agents.
It has been ob~arved that when the self-stripping coating compo~ition~ of the inventlon are to be e~ployed a~ pol~she~
and~or in o~her high glo~ formulations which are expo~ed to foo~ traffic, for ex~mple, floor coatings, lt i~ preferable that .
the composltions conta~n a wax. ~axiou~ waxes or mixtures o~
waxes can be emplo~ed which would be stable ln the overall ~ystem.
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L.
~48188 Such waxes ~nclude tho~e waxes der~ved ~rom a veqetahle, animAl, synthet~c and/or m~n~ral source or ~ixtures ~h~r~o~ Example~
of 3uch w~xe3 lnclude carnauba, candelilla, mont~n, lan~lln, cocoa butter, cotton~eed, ~tearin, Japan wax, bayberry, myrtl~, mace, palm k~rnel, be~swax, spermac~ti, Chine~e insect, ~utton tallow, polyethylene, polypropyl~ne ~ aY~es obtain~d by th~ hydro~e-nation of cocoanut oil or soyb~an oils, and the mineral waxe~
such as paraf f in, cere~in, ozokerlte, etc.
Par~icularly pre~rred waxe~ include mixtur~ of a polyethylen~ wax emul~ion and a polypropylene wax ~mut~ion, ~ach e~uls~on contalning about 25~ waxy ~olids. In general rom ahout 0 to 15% by wel~ht waxes are employe~ based on the wei~ht of al~ali soluble resin solid~.
The composltion~ of the present lnvent~on may al~o include a 5~all percentage, i.e., fro~ 0 to 10~ of a ~11~ modl~ying polymer.
These ~ilm-modify1ng polymers are higher molecular welght material~
~ith ~Jeight avera~e molecular welght~ aho~e 40,~00 and often in excess of 200,000. ~he~e ~aterials can be included to modify the perfoxmance char~cterist~cs o the re~ultant film3 and pxovide the ~lm~ w~h add~tional wear resi~tance, toughne~, etc. }Ilgh le~ls of these ~ater~als must be avoidea ~ince the h~gh p~I o~ the product cau~es these high molecular welqht polymers to ~ecome quite viscou9 which inhlbit.s the ability of compo~ltlons contalnlng these material~ to ~e truoly s~ tripplng~
Althou~h ~he solvent, plast~ci2er, ~ur~actan~, le~e~ing agent, wax, film-r.~odi~yin~ polymer or any co.~bi~atlon of the~e may be omitted ~rom the coT~position, the combined non-volatlles o~
the~e non-resin r.laterial~ ~ust be pre~ent in ~n amount at lea~t equal to or greater than 9% o~ the non-~olatiles o~ the polymerlc coating agent or resin ~or adequate per~ormance and fil~ propertles~
~lthoug~ ~here i~ no real upper limit at pexcentage~ over 200~, the ~el-~tripping proportie3 are reduced. Pre~erably, thiR percentag~
i~ le8s than 100~.
.,i~
8~
The composition~ of the present lnventlon ~re ~urther character~zed ~y the abs~nce o~ complex salts o metals which temporarlly cro~link the res~n~ Thes2 s~lt~ as dlsclosed $n U. S. 3,308,087 and 3,320,196 are not required to impart self-st~ipping properties to the compo~itions of the present invention.
Th~ compo~ition~ are generally adapted to form clear, glo~sy coat~ngs. 'lowever, if aeslred, a translucent appearance or an opaque or colored appearance ~ay be obtained by the intro duction of dulling agents, water-~oluble or oll-soluble dyes i~ suitable proportionsa Also, o~her non-essen~al co~ponent~
such as p~rfume~ may be ~ncluded in small amounts, The compositions of tha inventfon may b~ used for lmpreg-natlng textiles, leather, paper or other porous or ~ibrous materi-als. They may al~ be appliea to plastic sheet~ such a~ cellophane 9 polyethylene~ polyethylene glycol terephthalate, ~aran and the l~k~. ~hey may also be appl~ed to rig1d surac~s, including ~etals, such a~ steel, aluminum, copper, tln, wTough~ iron and pa~nted ~urfaces such as auto bodies. The compositions oan also applied to wood, ~ton~, br~ck, gla~, cem~nt, asbestos shingles or ~idlng, terrazzo, and concrete surfacea, such a~ 100r~ and the like. The compositions are part~cularly preferred for pol-iqhing floors and plastic tiles, such as linoleum, asphalt vinyl and vinyl-as~esto~. :
I~ generalO the ~ngrea~ents may be admixed $n the order de~ired. ~here a wax is employed ln the coating compos~tions, it 1~ usually added to the composition in the form o~ an emulsion.
Typical wax emulsion~ contain approximately 20 to 40% hy w~ight sol~ d and are formed by di~perslng the wax i~ water by means of a suitable an~onic or d~spersin~ agent. s~itabl~ agent3 ~ncluae sodlu~ ~alts of hlgher fatty acid ~ulfate~, the higher fatty acid 8alt8 ~ ~thylene oxide modified alkyl phenol~ and other con---- r:
.
' t ,':, ,;'" --' ~a8~L88 ventional dispersing agents. Particularly useful dispersing agents include amine salts of soap, such as ethanolamine or - morpholine oleate or stearate.
. .
The coating compositions can be applied to numerous substrates as set forth hereinbefore by various methods including application with a rag, mop, brush, non-woven cloth and by spraying and/or dipping.
The following examples are provided to further illustrate the present invention and are not limitive of '~
scope.
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:
" EXAMPLE I
S~ To demonstrate the effectiveness of the present ~ invention, several self-stripping coating compositions .
~-, were prepared. Unless otherwise stated, the weights of .,.~, .
~ the ingredients are in parts by weight.
. .
PARTS/
COMPONENT PARTS NON-VOLATILE
~ Styrene Acrylic Acid Resin : Solution (20~) 58.800 11 760 20 Tributoxyethyl Phosphate0.600 0 600 Oleic Acid 0.600 0.600 Octylphenoxy Polyethoxy Ethanol (70%) 0.686 0.480 Polyethylene Wax Emulsion (25%) 1.680 0.420 Polypropylene Wax Emulsion (25~) 0.560 0.140 ~ Pentel ~ 3611 Fluorochemical 0.020 ----~ Concentrated Ammonium Hydroxide 1.400 ---Water 35.454 ---Perfume 0.100 ---Dye at 1% _0.100 ---; 100.000 14.000 The pH of the composition was 9.6. The bulk of - the non-volatiles were derived from the styrene-acrylic acid resin solution with the other percentage of non-volatiles being 19.05% of the resin non-volatiles (non-resin non-~olatiles). The resin was a low molecular weight acidic copolymer with a monomer distribution of 68%
48~
styrene and 32% acrylic acid, based on the weight ofcopolymer. The resin solids have an acid number of 180 to 190. The resin solution also contained minor quantities of a sequestering agent and hyclrogen perioxide for cosmetic purposes.
.
. .
, 1 0 .' - ~ ' `.' ", '"''.
. ' ' :
;.' ' ' . ' ', ''" ~
-17a-: :, . . . . .
.
8~
resin ~olutlon addlt~on~lly contalned 5~ o~ diet~ylen~ glycol ~onoethyl ether~
The composit~on had ~xcellent storag~ stab~ llty. ~he ~ composition wa~ applied to ~ vlnyl 100r by con~entlon~l mean3 and ;:
allowed to dry, The dried pol~h ~wa~ ~cuffed and scra~ched. A
- ~econd coat of pol~h wa9 applled to the dried coa~ and th~ 3cuff~
: ~nd ~cratche~ were readlly re~oved. The above compo~ltlon pr~vided . .
. a non-yellow~ng floor pollsh w~th ,exc~llent wa~er spotting re~
- ~ance.
.:
.'.- . .
. . EX~LE I~
A ~loor coatlng composit1on having the followlng formu-lation was prepared:
:: CO~O~ENT PAR~S BY WEIGHT
, ,; Polymer ~ 34.7% solid~* ~9.865 Water S7.816 .. ~mmonium ~Iydrox~de ` 3~500 Carb~tol fi~ ` 5 1% solution o~ Pentel~3611 Yluorochemical 0.500 ~rito ~ X-405 (7~% solids) 0.~23 ~ributoxyethyl Pho~phatef~ 0.576 . 25% solids emulsion of A ~ 392 Polyethylene Wax 1.~20 .
p~ ~ 9.70 ~on-volatiles ~ 12.0%
Non-re~in ~on-volatiles ~ 15~8%
* The ~ono~er compo~itlon of the polymer wa~ as follows:
Methylmethacrylate 46.~%
Butyl Acrylate 30.0 ~ethacrylic ~c~d 23.8%
Ac~d number o 155 and the molecular weights a~ detexmined by G.P.C. were .~ ~ 12~100 . ~Sw ~ 32tlO0 When thi~ formulation was ut~lized to coat a floor, the . ~ame was completely self-~tripplng and had good glos~ and leveling characteristlc~.
.
..
EXA~LE III
A ~tr~ppablQ floor ~oatln~ compo~ition having the ~ollowing foEmulatlon wa~ prepare~:
f~ ~
-- - r lr~4~
COMPONENT PARTS BY WEIGHT
~ Water 51.666 :~ Concentrated Ammonium Hydroxide 1.221 . Carbitol 4.568 Pentel ~ 3611 Fluorochemical (25%) 0.020 Triton ~X-405 t70%) 0.698 ~ Oleic Acid 0.610 - Styrene Acrylic Acid Solution (25.3%)* 36.623 Tributoxyethyl Phosphate 0.610 - AC ~ 392 Wax Emulsion (25%) 1.953 : Poly EM ~ - 20 Wax Emulsion (40%) 1.831 Perfume 0.100 ~- Dye (1%) 0.100 ., 100 . 000 ,;
. Non-volatile = 12%
Non-resin non-volatile = 28.3%
pH = 9.6 .
* The resin is 67.5% S and 32.5% AA and has :, an acid number of 180 to 190. The Mn is 3,600 ~ to 4,000 and Mrw is 7,000 to 8,000.
: When utili~ed as a floor coating composition, this formulation had excellent gloss and leveling character-istics and was self-stripping, relatively water-insensitive, and was reasonably durable in use.
': :
. EXAMPLE IV
A floor coating composition having the following . 20 formulation was prepared:
COMPONENT PARTS BY WEIGHT
Water 33.356 Ethylene Glycol 5.000 ~; Triton ~ X-405 (70%) 0.800 :: SMA ~ Resin Solution* (20%)51.450 Polymer Emulsion (35%)** 5.000 Tributoxyethyl Phosphate 0.840 :: AC ~ 392 Polyethylene Wax Emulsion (25%) 2.154 Concentrated Ammonium Hydroxide 1.200 Dye (1%) 0.100 : Perfume 0.100 ,, 100. 000 ~' pH = 9.75 Non-volatile = 14.0%
Non-resin non-volatile = 36.05%
: * Resin solution is 20% solution of SMA~17352 .- from ARCO ~. Resin has acid number of 260 to 280. The solution contains fatty acid and fluorochemical.
-~ ** The polymer is a 35% solids emulsion of a polymer with the following monomer distribution:
3~% methyl methacrylate ~- 52% 2-ethylhexylacrylate 9% methacrylic acid The molecular weight of the polymer is in excess of 200,000.
. ~, - This formulation, when applied to the floor as a floor wa~ or coating composition, had excellent initial le~eling and gloss as well as good gloss and leveling characteristics subsequent to the utilization of the same as a self-stripping cleaner. Furthermore, the sensitivity ;~ 10 to water and the durability to traffic were judged as good.
!
EXAMPLE V
A still further floor coating composition was prepared ha~ing the formulation as follows:
_l~PONENT PARTS BY WEIGHT
Water 33.488 Ethylen~ Glycol 3.870 Triton ~Y X-405 (70~) 0.800 Fluo~ochemical ~C ~Y - 420 (1%) 0.500 SMA ~Resin Solution (20%)*46.200 Polymer Solution ** 10.048 Tributoxyethyl Phosphate 0.840 Tall Oil Fa~ty Acid 0.700 Anionic AC ~392 Polyethylene Wax Emulsion (25%) 2.154 Concentrated Ammonium Hydroxide 1.200 Dye (1%) 0.100 Perfume 0.100 100.000 pH = 9.75 Non-volatile = 14%
Non-resin non-volatile = 51.52%
,~
* A 20%~solids solution of SMAW 17352 (supplied by ARCd~ ~ in H20 and NH40H. Resin has acid number of 260 to 280.
** A 20.9% solids solution of polymer in sol~ent, NH4OH and H2O. The polymer has a molecular weight of greater than 200,000 and the following monomer distribution:
42% methyl methacrylate 50% 2-ethylhexyLacrylate 8% methacrylic acid This formulation, like the formulation from Example I~, utilized ethylene glycol in place o~ the ,~
polyether utilized hereto:Eore. The floor coating composi- -tion was quite satisfactory as regards self-stripping . :, , properties and had good gloss and leveling characteristics as well as good durability to traffic and moderate water - resistance.
~, .
EX~MPLE ~I
A still further floor coating composition in accordance with the present invention was prepared having the formulation as follows:
COMPONENTS PARTS BY WEIGHT , , Water 52.272 - Ammonium Hydroxide 1.200 ~, Carbitol 3.783 Pent~l ~)3611 Fluorochemical(25%) 0.020 `~ Triton (~X-405 (70%) `0.686 Oleic Acid 0 600 Resin Solution* 36 919 , Tributoxyethyl Phosphate 0.600 -- AC ~) - 392 Wax Emulsion ~25%) 1.920 Poly EM ~) 20 Wax Emulsion (40%) 1.800 Perfume 0.100 Dye (1%) 0.100 100 . 000 , , pH = 9.6 -' Non-volatile = 12.0%
Non-resin non-v-~olatile = 31.59%
* Resin solution is 24.7% non-volatile and contains a solution prepared copolymer with the follo~ing monomer composition: 59% S, 10% BuA, 31% A~. Mw c 10,000.
;; This formulation performed quite adequately ., as regard to coating characteristics and especially self-stripping capacity, high gloss and leveling character-,, .
istics. The durability and resistance to water spotting ~, were good.
i~, EX~MPLE VII
I A still :Eurther composition in accordance with i, the present invention for use as a floor coating composition was prepared having the following formulation:
.. . .
~ --21--, , ~ . , .
~ . ,. . : . " . . . :
8~8~
~.`
` _OMPONENT PARTS BY WEIGHT
Water 39.060 Ammonium Hydroxide 1.396 Caxbitol 4.985 Pentel ~ 3611 Fluorochemical (25%) 0.020 Triton ~X-405 (70%) 0.800 - SMA ~ Resin Solution *48.055 Tr~butoxyethyl Phosphate0.598 AC~ - 392 Wax Emulsion (25%)4.786 Dye (1%) 0.200 Perfume 0 100 .~ 100 000 pH = 9.65 Non-volatile = 12%
Non-resin non-volatile = 24.85%
* SMA~ resin solutio~-is 20% non-volatile - and ~s made from SMA 17352A supplied by ARCO~Y. It has an acid number of 260 to 280.
- When coated on tile floors as a floor polish composition, the above composition showed excellent self-- stripping capacity, good gloss and leveling characteristics, as well as reasonable resistance to water spotting and adequate durability to traffic.
.::
EXAMPLE VII
A formulation having the concentrate composition as follows was prepared:
COMPONENT PARTS BY WEIGHT
~ater 53.731 r Ammonium Hydroxide 1.400 Carbitol 0 882 - Pentel ~ 3611 Fluorochemical (25%~ 0 020 ` Triton ~ X-405 (70%) 0.686 Oleic Acid 0.600 - Styrene Acrylic Acid Resin (20%)* 28.800 Polymer Emulsion ** 9.361 - Tributoxyethyl Phosphate 0.600 Poly EM OE~20 Wax Emulsion (40%~ 1.800 AC @~- 392 Polyethylene Wax Emulsion 1.920 - Dye ~1%) 0.100 Perfume 0.100 100 . 000 pH = 9.6 Non-volatile = 12%
Non-resin non-volatile = 120.93%
* The resin has an acid number of 180 to 190 and is 67.5% S and 32.5% AA.
': . . ' . ' . ' . ' . ' . ' ' ' i ' ' ' " ~ . ' ' . .. ' ' .. ** The polymer~emu-l~sion is 35%.non-volatile -~- a~d has the ~qllo~n~ monomer distr~bution: lU parts st~rene . 50 parts ~ethylmethacrylate 30 parts Dut~l acrylate .- 10.parts.methacrylic acid .
The molecular weig~ts of the polymer are as follows:
Mn = 4,200 Mw = 9,000 .
When the above formulat:ion was utilized as a floor - coating composition in accordance with the present invention, the same had excellent self-stripping capacity, as well as .
: good gloss, durability, and leveling characteristics. Also, the resistance to water spotting was adequate.
. EXAMP E -IX
. A composition in accordance with the present :. , .
:~ invention which is designed to be diluted with water before use : .. to approximately 2-20% solids was prepared having the following . ~ composition: `
.. . .
COMPONENT PARTS:BY WEIGHT
. Wa~er 32.03 Trisodium NTA 1.50 :"`
: Propylene Glycol 17~00 Pentel ~ 3611 Fluorochemical (1%) 0.50 .: Concentrated~Ammonium Hydroxi~e . 15.00 Water SolubIe Blue Dye at 1% 0.10 .20 Tributoxyethyl Phosph~te 1.59 ; Styrene~Acrylic Acid Resin Flakes* , 33.98`
~ Triton ~y X-405 1.90 :: Tall Oil Fatty Acid 1.59 ;~ pH ~ 9.6 Non-volatile = 40%
Non-resin non-volatile = 17.71%
* The resin is 67.5% styrene and 32.5%
; acrylic acid. It has an acid number of 1~0 to 190. Mn = 3,600 to 4,000 and Mw = 7,000 to 8,000.
;, . When the above formulation was diluted with water to ~, .
;. - 4~ soli~s, t~e d~luted composition had excellent self-stripping properties, ex~ellent dura~tlity, excellent gloss and leveling characteristics. Also, the re$istance to water spotting was good.
- -23- `
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When the above compoSition was diluted to 20% solids, -~` the results upon coating ~ere al~o ~ui~te good with the 20%
solids compo6ition having good ~elf stripp~ng action, high gloss and durability, as well as leveling characteristics.
Also, when the above formulation was prepared as a
BP~CK~ROUND O~ THE I~nrENTloN
.
The pre~ent lnvention xelate~ to stable, aqueous coating compositions. In partl~ular 1:he lnventiorl relate~ to ~n lmpro~red 8tZl~le aquaou~ coat~ ng compo~lt~on containing a~ the prim~ry coatfng agent an alkali ~oluble rl38ill oiE low molecular weight and high ac~d num~er and aqu~ou~ ~rmnonia ~uific~ent to proYide a p~l no le~ than about 9 . 0 .
In the protective coating ~ield, such a~ temporary oxganic coating~, including certain f loor coating~ J ~ t ~ des~rable to haYe m~ n~mum carboxyl ~unctionality pr~en~ in oxder to avoid h~ ~olubili~ing and ~potting efîec~s nor~ally obtalsed wh~n water ~8 brought into contact with su~h coating. t~owever, the hardnes~, durability, gloss, and removability propertie~ o~ th~se ~llms are ~ffec~ed by th~ degr~e of carboxyl functionaliSy present. There-~vreJ mo~t coating compo~ on~ de~eloped here~o~or~, represen~ a compromise with re~pect to prope~tles ~u~h a~ hardne~, duxability, ~10~5, removal~ility, and xe~istanceO
~: It ha~ been found th~t YariOU~ organ:5c fllm~ contalnin~
carboxyl functional~ty suffici~nt to obtaln ~s~sy removal, tend, - upon aging, to und~rgo a degrading e~fect; that i8 a 10~8 0~
functionality which xender3 th~ carboxyl ~roup~ ~ubstantially `
unavallable. Thi~ degra~ln~ ect produce~ 1~ms wllich are dl~ficult to ren~o~re by means o~ conventional film remov~r sub-stance~, such as de~ergents, and re~ult~ in ~llm bulldup. Film buildup is usually accompanied by degrada~ion. in color9 for example~
y~2110wing, and ev~ntually necessita~es complet& ~ilm removal w~th hi~h caustlc ~olutlons or 80'l ~tions containing organic solventEI or by variou~ abrasive method~, all o which have been found to e~ect the sub~trate ~dversely.
The problelD of removability, degradat~on and fllm bu~ld-up was alleviated greatly by the u~ o~ the mi~t~l crosR-linked , :`~
polym~r~ di~clos~d in ~.S. Patent~ 3,308,a78 and 3,320,1~6.
The metal ~omplex salts d~sclo~ed in the above patent~ ~orm tempoxary bond~ or cro~s-link~ b~tween ad~acent polymer carboxyl funct~onal group~ ~o aB to retard their exposur~ and sub~equent degradat~on.
These 1vor coating composi~ion~ provided fllms w~th good glosa and strength which could be e~sily removed by cleaning with d~ter-gent and ammonia but are water in6ensit~ve and detergent resls~ant under no~mal co~di~ions.
For many applications, among them the ho~, it has been deemed desixahle to malntain hl~hly poli~hed ~loox ~urfaces fQr ae3th~tic appeal as well as ~or other rea~on~. In lleu of detergent-cleaning a y~llowed or d~rty floor f~lm, it i~ ~onsidered hiqhly de~irabla to merely recoat and thereby ~lmultaneou~ly clean and remove the old polish layer and onm a new ~il~. Accor~-ingly, the ~eed has arisen for a ~elf-str$pping ~loor polish adapted to be frequently reapplled to main~ain a hi~hly polished ~ub~tratc which i8 not to be wa~hed with detergen~ between appllca-tions. The polish must have non-yellow~nq ch~racteri~tlcs and be ~hel~-stabl~O
Re~er~tly, various innovatlons have been ~ntroduced permitting a drled floor coat~ng to be ~imultaneou31y cle~ned and polished without th~ need for conventlonal washing and repol~
~3hing, and withou~ f~lm buildup. As illustrated in U.S. Patent 3,308,0~8 ~odiications in the ab~a type o~ f~rmulation can prvduce a st~ble, aqueou~ coating compo~itlon whlch provide metal-contsining organic fiLm~ having unique ~tructural int~grity;
captive functional groups which are not easily degraaed; controll~d removability and high ylo~s, hardne~s and durab~lity. These coatings are designated as sel-~en~itlve coating~ and after appl~cation ~re resistant to detergent washlng and can ~e re~o~Qd hy recoating. Upon recoat~ng, a portion of the dried ~ilm i8 ;~
~9L8~L~8 -.; dlspersed i~ the f resh coat~ ng and a n~w coating i5 provid~d whLch is substantially ~ree ~rom the heel mark~, scuffs, and oth~r dirt contained ~n the old dried coatlng.
:
The ~table sel~-~tripping aqueou~ flovr ~oatin~ co~po-s~tion of the presen~ invent~ on co~prlses ~s ~he pr~mary coating agen~ a solut~on of an al~al~ ~oluble resin having a weigh~ av~r~ye molecular welght of front about 500 to about 4~,OOO and an ac~d number withln the range of from 120 ~o ~50. ~hi~ al~ali soluble re~ln is an addition res~n conta~n~n~ at lea~t two ethylenically unsaturated monomers, one of ~hese monomers be~ng a ligand-free mononter while the other monomer contains carboxyl functlonal group~. The coating c~mpos~tion o~ thQ pre~ent inventlon also include~ aqueou~ ~monia in a concentra~lon ~uficient to provide a pH o~ no less than about 9.O and a com~ined amount of wax, olvent, level~ng agent, surfaatant and hlgh molecul~x weight polymer equal to or greatar than 9~ ~y wei~ht of the r~sin.
Thi~ co~position i5 raadlly adapted to dispers~ a previously depo~ited dried coating compo$it~on of lt~el~ and replace th~
dr~ed coating with a fresh aoatlng having even glo~ ~nd durability.
.
SU,~RY OF T~E INV~NTION
~ t i8, therefore, a primary ob~ect o~ the pxe~ent lnven-tion to pro~ide an ~mpro~ed ~el~ ripping coating compo~ition.
It ~8 ~ ~urther ob~ect of the invention to pxovide a sel~t~ipping coating compo~ition fxee from the tendcncy to gel and change visc03ity upon storageO
It i~ a further ob~ect o~ tho pre~ent invention to pro-vide a ~imple ef~icient ~elf-~tripping composition which doe~ not contain any metal complexing agent.
It i~ another ob~ct of the invention to provide a coating composition sdapted to remove deep scuff~ and scratche~ fror.
previo~ly poltshed floors upon recoating.
`:
L
~48~
It is an addltional ob~ect to provlde a ~elf-~3trlpping coating compos~tisrl adapted ~o dlsper~e a previously applied coatlng ~nd to recoat a sub~trat~ wi~h ~ub~ntlally a slngle layer of n~3w coa~ing ~ilm, thereby reducing 02 elimlna~ing 'che bulldup ~n ~ilm thic3cne~ that characteri~e~ conYentional ~loor pollsh~s.
St~ 11 fur~her ob~ects and advantages o~ the floor poliF~h compo~ition of th~ present inven~ion w~ 11 become more apparent Prom the following more detailed descriptt on th~x~o~ .
DE~INITI()N5 ~ or the purpo~e~ of the pre~ent invenl-ion a "stable"
corRpo~ltlon i~ defined a~ ~ fluid substance which can be storQd ~or prolonged periods and i~ subs~anti~lly free from gelling and substantially free from changes ln viscos$ty. It i~ e~serl~ial tha~ the ~el~-stripping coating compo~itton~ of the inven'c~on be ~t~ble~ In ord~r to obtain the ~elf-strippi~g ilms of ~h~
~nv~3ntion a~d in oxder ~o dl~per~e a ~ubs~antial amount o~ the film, th~3 self-~trippiz~g coating c:ompo~ tion mu~t b~ ~ub~tantl~lly fxee fro~n gellation and/or precip~ation and hav~3 substan~lally ~be sam~ composltior~ throu~hout.
, . . . . .
The ~tab~l;lty of the presently claimed ~elf ~tripping coat~ ng composit~ ons can be monitor~d hy per~ odic optical den~ity ~easurem~nts and can be verlfled by monitorillg phy~ al change~
i n the compo~ltions durln~ prolonge~ cc)ntinuous exposur~ At high temperature c:ondit~on~. Procedure~ for monttorln~ optical dan~ity and phy~ical cha~qes are ~llustrated ln U.S. i,308,0780 ~ 8 employed h~r~n, the te~ H~elf-str~pping" r~2r~ to thæ a~llity o~ the in tant coat~ ng composition~ to react with a f~m obtained from the c~;nposi tlon and to disper~e a -~ubstantial quantity o~ tha film ~n the liquld coating composition in les~
than half a mirlute. Alhs~, the term "~multan~ously", when used _5_ L
8~8 to describ~ a "sel~-stripping" compositiorA, mean~ the compo~l~ion di~per~e~ in les~ than hal~ a ~l~ute.
As employad hereln, the "acid n~r" o~ the r83in8 used ln the pre~ent inventiorl 18 th~ actual ox obsex~ed valu~ a~ di~-tlngu~ shed ~rom th~ th~oret~cal value and can be ob~erved by dls-~olving the xesin ~n a solutlon conta~ning 66g~ by weigh ethanol and 34~ by weight ben2ene and titrating th~ resin/solvent mixture to the phenophthalein end polnt with a 0 01 W a~ueous ~0~l 601utionO
~ha~ gener~l procedure i~ described by Pinner in "Pract~ ~1 Cour~e in Polymer Chemistry" ~1961), F~rgamon Pxess, ~ew York, New York, at page 113. ~t ls understood ~or ~h~ purposes o~ ~he pre~ent in-r~ntion that the ten~ "acid ~alue" can l~e u~ad inter~:hang~ably w~Lth the torm "ac~d m;mber".
DEq~AILED DESCRIPq~TON O:l? T~E ~ NTION
The pre~ent iAvention i.~ dir~cted to a ~table coatlng compo~i~ion adap~ced to ~im~ltaneou~ly dl~per~e a pre~ou~ly deposited dried coat~ ng r:ompo~ition and replace the drl~d compo -8ition with d iEre3h coating comprising 50-96% by we~gh~ watsr, 0-1096 by welght pla~tlcizer, 0~ by weight l~veling agent, 0- la~6 by we~ght or~anic 301vent, 0-5% by weight ~ur~actant" 0-15~6 by weight wax, 0-10~ by wei~ht ~ilrn-rnodifying pol~ner and 3-18P~ by weight polymer.Lc coating agen~, with th~ pro~ 8C~ that the total non-volatiles of the compo~tion 13 ~n the rang~ o ~rom 4-20~
by weighlt, a:nd ~he com~ined non~volatlles of the leveling agent, solvQnt, p~ticizer, surfactant, wax and f~ lm~modi~yin~ polymer ar~ equal to or greater than 9% of the non-vc3atile~ of the polymer~ c coat$ng agent wherein the lmproveTnent co~prise~ u~n~
a~ the pol~;leric coatinS~ agent a 801ut~0n of an allcali soluble x~ln having a we~ght average molecular weight from about 500 to ~$0, 000 and an acid number ~rom about 120 to 550, sa~d resin baing an addition resln ~ormed frc~m ta) at lea~t 1 ethylen~cally ~` ~
1318~
un~aturateà ligand-free ~nonomer and (b) at laast 1 ethylenlcally un~aturated mono~ner h~ring at lea~t 1 carboxyl group, whsrein sald resins contain from abou1: 40-8~ by welght of monomer (a) and ~rom 60-lS'g by weight monomer ~b~, adding a~ueous a~nnonia to ~aid composition in an amo~mt sufficient to provlde a pE~ of no le~s than 9. 0, and said composi~on belng sub~antially ~ree o~ complex salt~ oî cro~3-linking metals ~uch a~ zinc, cadimum, copper ~ etc ~ he pre~erred 8elf strippi~g 5tab~e coating compo~itions of the present invention ars aqueous compositlon~ cc: ntaining pre~erably from about 4~ to about 18% rlon-~rolatiles . Particularly enhanc~d g~loæs and ~elf-stripping characterist~c~ are obtain~d when the aqueous cornposltion contain~ ~rom about 10 to 14~ non-volatiles by weight.
In addition to the abo~e ~e~f ~tripping stal~le coating compo~ ion~ containing from about 4~ to 20% non-~rolatlles, the composition of ~he present in~rent~on may also be p~repared in a concentrated or bucket-dilutable ~orm containing up to about 55~ ~olid~. O;E course, these concentrated cornpo~ition~ are de~lgned to be diluted during use to a composition havin~ a solids cont~nt batween 4% and 20B. Alternativelyt the concentrated product may be airectly appl~ed to the ~loor and subsequently ~opped or diluted with a wet mop.
Th~ ~ucket-dilutable ~ompositio~ o~ th~ present inventlon util~ze the same materials in the same re~ative ratio~
The only di~:eQrence i~ that the ~olids level is greatly incxeased whlle the water level ~ reduced. These composltions co~prise 20-50~ by weight water, 0-20~ by w~ght plastici~er, 0-10~ by weight leveling agent, 0-25~ by we~ght organlc solvent, 0-20~ by we~ght sur~actant, 0-20~ by weight wax, 0-20~ by weight ~il~
modi~ying polymer and 18-45~ by weight poly~eric coat~ng a~ent at a sol~d~ level o ~rom 20 55~.
~ he resin~ ~or u~e R~ th~ polymeric coatlng agent ~hould be alkali soluble and contain at least about 0.0021 e~uivalent of carboxyl ~ro~p~ per gram of res~n and be ~apabl~ o~ being substantially compIet~ly ~olubilized when a minim~m of ~rom about 80 to 90~ o~ these carboxyl groups ar~ neutralized with an aqueou~
801utlon of ba~ic substances ~uch as borax, a~ines, ammonlum hy~rox~de, sodium hydroxide and/or pota~sium hydrox~d~. ~or example, a ~uitable styrene~acrylic acid xesin ha~ing ~n acld number o~ about 190 would contain no le58 than about 0.0034 equiva-lent o~ carbo~yl groups per gram o~ resin and w~uld be ~u~tantially completely solubillzed when a mi~imum of ~rom about 80 to 90~
~f the caxboxyl ~roups are neutralized by an aqueou~ base solutlon.
The alkal~ soluble re~ins u3eful ln th~ composition ¦of the present invention axe addition re~in~ co~tainin~ at lea~t two ethylenically unsatura~ed monomers. One of these said monomers should be a hard monomer, sometlme~ referred to as the ligand-~rea mo~omer. The o~her monome~ should be a ligand-conta~nlng polymerizable monomer providin~ the necessary acid ~untlonality which contribute~ substantially to filM per~vrmance and ~s~i8t8 in ~aintaining ~uch des~rable propertie~ a~ film hardne~s, glos~, durability and controlled removability.
The acid number o~ the low~r molecular we~ght alkali 901~ble xe~i.ns i5 critlcal and influences both the ~olub~lity o~ the xe~ins in the aqueou~ al~aline coatin~ compo~itions and al80 th~ sel~-xtrlppin~ properties o~ the film~ produced ~ro~
the~e compo~itions . For example ~ at an acid number substanti~lly b~low about 120, certain of the add~tion res~ns are rela~ively in~olubl~ in the aqueous coat~ng cvmpo~itions o~ the inve~tion.
Al~o, at the~e low acid n~ber~, the films ~ormed from such resin5 are not readily self-~trippa~le and deter~en~ and the like mu~t be ~mployed with high alkali content to remove films ~oxm~d from 8~
~uch re~ ns. When the acid number o~ the addition resln i~ substan-ti~lly above a~out 550, th~ ~ilms ~orme~ from such coatlng cotnpo8~-tion3 tend to be high~y sub~eo~ to wa~er spotting. Accordingly, for the fiel~ s ripping coatlng ~o~posltion~ the acid value oiE
th~ addition resin ranges betwe~n 120 and 550, between abc:ut 150 and 300, and most pre~erably will ran~e ~xom about 150 to a~out 250.
~ he molecular weight o~ ~he alkali xoluble resin~ of the invention 15 also critical. The generally low molecular weight of the p~eerred polymers keeps the viscosity o~ the coating compos~tion w~thin acceptable limit~. ~he ViBCo8ity of a ~olution of the alkali ~oluble polymexs is stron~ly dependent on the pH, on the aci~ n~ber, a~d on the molecular weight o~ the res~n~.
~8 stated hereinaboYe~ it is necessary to keep the pH o~ the coating composition at a relatively high level~ Ther~fore, to control vlscosity and to ~ ncrease the ~esin ~elf-strippins ~ it ha~ been ~ound tha low molecular weight polymer~ are necee~ary.
The preferred molecular welght for a speciic al~cali ~oluble re~in is, in p~rt, dl~tated ~y its aaia nu.~er, the p~
o~ the coating composition employing the resin and the percentage o~ ~olids in the coating compo~ition . To assist ~ n the disper~ion of the dried film upon recoating, to control ~rlsco~ity at ~ low level and to enhance the glo~ of the pre~erred coating compo~itions, re~ns having a w~ight average molecular weight ~rorr about 500 to 40,00D ~hould be used, wlth polymex~ having a molecular we:lght o~ 500 'co 30, 000 being preerred and those w~th a molecular we~ght s>~ 500 to lO,OOO ~eing mo~t preferred slnce enhanced result~
are obtained.
For the purpo~e~ of the pres~nt invention, the ligand-~ree r.lonomer should be free from any atom~ mol~cule, or lon capable of ~or~3ing a coordlnate bond, such as a carhoxyl ion . Suitahle ligan~ ree monomer~ must also be c~pa~le of undergolng additlon -.
` `` 3l~48~L138 ~ polymerization. The resins should contain from 40 to 85%
.- ligand-free monomer and preferably 40 to 75%.
If desired, the ligand-free monomer can be a mixture of monomers. Exemplary of such ligand-free monomers ~ are vinyl toluene, methyl methacrylate, butyl methacrylate, --~ acrylonitrile, vinyl acetate, styrene, 6~ -methyl styrene, .. .
butyl acrylate, ethacrylate, 2--ethylhexyl acrylate and mixtures. Other suitable monomers and comonomers are disclosed in U.S. Patent 3,308,078, columns 9 and 10.
~;j 10 The ligand-containing polymerizable, ethylenically unsaturated monomer utilizes carboxyl groups as the prefer-red polymer ligand. Preferred ligands are ethylenically unsaturated alkanoic and alkandioic acids, particularly those having 3 to 8 carbon atoms. Examples of preferred acids include acrylic, methacrylic, crotonic, isocrotonic, maleic, fumaric, itaconic acids and anhydrides of these acids, as well as mixtures thereof.
;, '. ! , Stability and self-stripping of the coating compositions are enhanced; and, accordingly, it is ~
;~; 20 preferred to employ an alkali soluble resin containing ~!' acrylic acid, methacrylic acid, or mixtures as the ~- ligand-containing monomer.
In general, the minimum weight percentage of , . . .
ligand-containing monomer in the alkali soluble resin will be determined by the amount of acid functionally necessary to give the resin required alkali solubility in aqueous media. E'or most purposes at least about 15%
and preferably 25% by weight of resin of ligand containing monomer is employed. The maximum weight percentage of ligand-containing monomer is determined by a combination of various factors; among them viscosity of the resulting composition, water spotting sensitivity of the dried coat ::-- ~ -10-.. :, . ~ ' ' ', .
: . , , . resulting from the coating composition and tackiness of .: the resulting film when the coating composition is : applied to a subtrate.
,~
, ,.
-lOa-10481~ 1 In gQneral up to a~ou~ 60% by wel~h~ l~gand-containing mOnomQr may be employed ~n the re~in. A~ove about 60% monomer ; the r~ultlng coating composlkion t~nd~ to become exce~ively .- vi5cou3 dur~ng storage and during use- Furthar, the dried ~
-~i re~ulting whQn the coating compo~ition contalning the mono~er :
` i8 applied is excesslvely watex sensitive and will have a tendency :
to ~pot unduly.
Al~hough any combination o~ the above monomers ~ the ranges set orth above which ~orm~ a continuous ~ilm will be suitable for use ~n the sel~-~tripping f~nish of the present invent~on, resins ~ade from the followin~ co~bination~ of monomer~
are preferre~: styrene/acrylic acid; styrenefmaleic anhydride;
methylmethacrylate/butyl acrylate~methacrylic acid; ~-methyl-styrene/ethyl acxylatefacrylic acid; 3tyrene/~utyl acrylate/acrylic acids and styrene~methyl methacrylate/butyl acrylate~methacrylic acid.
A pre~erred alkali solublQ resi~ i~ a 68% styren~/32 acrylic acid re~in having a wQight avera~e molecular weight of about 500 to 10,000. Other pre~erre~ addition r~in~ include a partially Qsteriied ~tyrene-maleic anhydri~e resin hav~ng a~ acid numhex o~ about 200 and a molecular w~iqht of about 1400 and a 45% ~-methyl~tyrene/3C% ethyl acrylate/25% acrylic acid having an ac$d nu~.~er of lS5 and a weight averaye molecular weight o~ 5,000. In general, styrene-acrylic acid resins havin~ number averag~ molacular weight~ ~rom about 2,500 to 4~500 and weight av~raye molecular welght~ o~ 6,500 to 9,500, a~ well a~ an acid number of 170 to 200, are particular preferred.
~ queous amm~nla i~ present in the coatlng composl~i~ns o~ the inventlon in a concentration su~ic$ent to pxovide a pH
of a~ least about g.0 and preferably above ~.S. It ha~ been found ~hat th~ hicJh p~ level subst~t~ally cnhances the 5~1-s~ripp~ng character o~ th~ compo~ition. Amm~n~ may be providcd in the coatlng compo~ition in the form o~ concentrated ~monium hydroxide. A portion or all o~ the ammon~m hydroxlde may be r~placed wlth sodium or potas~lum hydroxide or organia aminQ.
I;ow~ver, such r~placement is u~ually accompanied by a decrease ~n th~ water resist~nce (spotting resistancQ) o the product.
i In order to enhance the characteristics of a Pilm ~ormed `; ~rom the instant coatin~ compo~ition from 0-10~ by weight o~
:.................................... .
::- - a polyhydroxy polyether~ a lower alkanol or h~gh-~olling ~lycol , '~ i3 pre~ent in the present composition~ These organic solvents aid in extending the drying tlme of the coat~ny composltion and impart~ increased gloss and 1QV~1ing characteri~tics to the comp~-si~on. Typ~cal polyethers ~nclud~ mono- and di-alkyl ethers -~ o~ diethylene glycol and their derivatlves, also ~nown as car~itol~O
:- Typical glycols are e~hylene glycol, polyethylen~ ylycol, propylene glycol~ polypropylene glycol, etc~, while the alkan~ls inc~ude - i~opropanol, hutanol, etc. ~ p~rticularly preferred polye~her , .
is d~ethylene glycol monoethyl ether. mh~ polyethers can be used alone or combin~d with the alkanol~ or polyhydr~c alcohol~, such as ethylena ~lycol.
The film fonming c~mpositlons ~ay contain from about O
to 10~ by weight plastici~ers wherever nece~sary, to provide a of suitable h~rdne~s and appearance. It has been ~ound ~ha~
most hard ~e.sins can be pla~ticized to improve their ~llm ~ormin~
properties. Since the purpose of the pla~ticiz~r ls to impart ~lm osming properties to the coatin~ col~position ana since it 18 not always necessaxy to impart flexibillty to the resin composttion wllen it is inherently tou~h and fle~lble, a ~ug~tive or ~e~i-fugitive plasticizer may ~ometimes be employed rathar th~n a permanent plasticizer. ~iixtures of fugi~ive and permanent pla~ti~izers may also be employed.
~ xamples of essen~ially permanent plasticizers that ar~
~uitable lnclude benzyl butyl phthalate, ~ibutyl phtha~ate, . _~ L,.
1~818~3 dimethyl phthalate, triphenyl phosphate, 2-ethyl hexyl benzyl phthalate, butyl cyclohexyl phthalate, mixed benzoic acid and fatty oil acid esters of pentaerythritol, poly (propylene adipate) dibenzoate die~hylene glycol dibenzoate, tetrabutylthiodl-succinate, butyl phthaly butyl glycolate, triethyl citrate, acetyl trlethyl citrate, tributyl citrate, acetyl tributyl citrate, dibenzyl sebacate, tricresyl phosphate, toluene ethyl sul~onamide, the di-2-ethylhexyl ester of hexamethylene glycol diphthalate, di-~methylcyclohexyl)-phthalate and tributyl phosphate.
Exampl,es of fugitive plastici2ers include the monethyl or monomethyl ether of diethylene glycol, isophorone, benzyl alcoh~l, and 3-methoxybutanol-1. The particular plasticizer amount thereof employed are chosen in accordance with the demand for c~mpat~b~lity and efficiency by making the fi~m more flex1ble.
A particularly preferred pla~iaizer which al50 serves a~ a leveling ag~nt is tributoxy,ethyl phosphate.
An extremely desirable ingredient in the present coating compositions which serves as a leveling agent and a self-sensitiæer of the composition is a sur~actant. I~ is preferred to employ anionic or nonionic sur~actants and part~cularly non-~oaming surfactants to reduce the tendency of the coatlng composition to form bubbles upon application. The sur~acta~ts increase the storage stability o~ the composi~ion and permit even film formation of the coating composition upon application (leveling).
Usable water soluble, low foaming'nonionic surfactants include organo-ethylene oxide condensates as described in U.S.
Patent 3~308,078, in columns 21 and 22.
' , Example~ o~ suitable low foaming anionic sur~actants in~lude alkali metal and ammonium salts of higher ~atty acids havlng 12 to 22 carbon atoms. Typical anionic surfactants include the sodium, potass~um, ammonium and morpholine oleates, ricin-oleate~, ~tearates or i30stearates.
1~48~B8 .~' Mixtures o~ an~onlc and nonlonic sur~actants may be : employed. Enhanced result~ are obta~ned; and, accordingly, lt is ; preferred to employ a ~xture o~ olQiC acid and octylpheno~y ~` polyethoxy ethanol as surfactants.
~; Th~ uantlty of sur~ac:tant~ employed will depend in part upon the character~ st~ C8 of the al~ali soluble resin . In general ~: from about O to 5~ by weight surfactants are employed based on the weight of the total co,~pos~t~on.
I~ desired, the pre~erred plastici~er and surfac~ants , , .
can be replaced in part with dibutylphthalate; however~ the glo~s and leveling characterist~cs o~ the resulting films are impalred s~mewhat.
In addition to the sur~actants and plasticizers, alkaline bullders such a~ the ammonium and alkal~ metal salts of ethylenedi-am~na tetraacetic acid, nitr~lotriacetic acidf diethylenetriami~e- ::
pentaacetic acid, citrio acid, and the phosphonates can be opt~on-ally included to pro~ide 3tab~1ity and improved cleaning character- ~-~stic~ 3n an amount o~ from O to 5~ and pre~erably 0 to 2~.
In addition to the levelin~ ~unction of some pla~t1cizers and surfactant~, the compos~tion o~ the presen~ ~nYention al80 may inc:lude from O to 5% o a leveling agent to assi~'c the cor~po-sltion ~n level~ny over other finishe~ such as the fluorochen~cal leveling agents disclosed in U. S. 2,937,098, gelatine, perfluorinated cyclo-compounds disclosed in U. S. 3,163,547, and other known leveling agents.
It has been ob~arved that when the self-stripping coating compo~ition~ of the inventlon are to be e~ployed a~ pol~she~
and~or in o~her high glo~ formulations which are expo~ed to foo~ traffic, for ex~mple, floor coatings, lt i~ preferable that .
the composltions conta~n a wax. ~axiou~ waxes or mixtures o~
waxes can be emplo~ed which would be stable ln the overall ~ystem.
' -14~
_..
. ' . : .. ' ~ . :.
L.
~48188 Such waxes ~nclude tho~e waxes der~ved ~rom a veqetahle, animAl, synthet~c and/or m~n~ral source or ~ixtures ~h~r~o~ Example~
of 3uch w~xe3 lnclude carnauba, candelilla, mont~n, lan~lln, cocoa butter, cotton~eed, ~tearin, Japan wax, bayberry, myrtl~, mace, palm k~rnel, be~swax, spermac~ti, Chine~e insect, ~utton tallow, polyethylene, polypropyl~ne ~ aY~es obtain~d by th~ hydro~e-nation of cocoanut oil or soyb~an oils, and the mineral waxe~
such as paraf f in, cere~in, ozokerlte, etc.
Par~icularly pre~rred waxe~ include mixtur~ of a polyethylen~ wax emul~ion and a polypropylene wax ~mut~ion, ~ach e~uls~on contalning about 25~ waxy ~olids. In general rom ahout 0 to 15% by wel~ht waxes are employe~ based on the wei~ht of al~ali soluble resin solid~.
The composltion~ of the present lnvent~on may al~o include a 5~all percentage, i.e., fro~ 0 to 10~ of a ~11~ modl~ying polymer.
These ~ilm-modify1ng polymers are higher molecular welght material~
~ith ~Jeight avera~e molecular welght~ aho~e 40,~00 and often in excess of 200,000. ~he~e ~aterials can be included to modify the perfoxmance char~cterist~cs o the re~ultant film3 and pxovide the ~lm~ w~h add~tional wear resi~tance, toughne~, etc. }Ilgh le~ls of these ~ater~als must be avoidea ~ince the h~gh p~I o~ the product cau~es these high molecular welqht polymers to ~ecome quite viscou9 which inhlbit.s the ability of compo~ltlons contalnlng these material~ to ~e truoly s~ tripplng~
Althou~h ~he solvent, plast~ci2er, ~ur~actan~, le~e~ing agent, wax, film-r.~odi~yin~ polymer or any co.~bi~atlon of the~e may be omitted ~rom the coT~position, the combined non-volatlles o~
the~e non-resin r.laterial~ ~ust be pre~ent in ~n amount at lea~t equal to or greater than 9% o~ the non-~olatiles o~ the polymerlc coating agent or resin ~or adequate per~ormance and fil~ propertles~
~lthoug~ ~here i~ no real upper limit at pexcentage~ over 200~, the ~el-~tripping proportie3 are reduced. Pre~erably, thiR percentag~
i~ le8s than 100~.
.,i~
8~
The composition~ of the present lnventlon ~re ~urther character~zed ~y the abs~nce o~ complex salts o metals which temporarlly cro~link the res~n~ Thes2 s~lt~ as dlsclosed $n U. S. 3,308,087 and 3,320,196 are not required to impart self-st~ipping properties to the compo~itions of the present invention.
Th~ compo~ition~ are generally adapted to form clear, glo~sy coat~ngs. 'lowever, if aeslred, a translucent appearance or an opaque or colored appearance ~ay be obtained by the intro duction of dulling agents, water-~oluble or oll-soluble dyes i~ suitable proportionsa Also, o~her non-essen~al co~ponent~
such as p~rfume~ may be ~ncluded in small amounts, The compositions of tha inventfon may b~ used for lmpreg-natlng textiles, leather, paper or other porous or ~ibrous materi-als. They may al~ be appliea to plastic sheet~ such a~ cellophane 9 polyethylene~ polyethylene glycol terephthalate, ~aran and the l~k~. ~hey may also be appl~ed to rig1d surac~s, including ~etals, such a~ steel, aluminum, copper, tln, wTough~ iron and pa~nted ~urfaces such as auto bodies. The compositions oan also applied to wood, ~ton~, br~ck, gla~, cem~nt, asbestos shingles or ~idlng, terrazzo, and concrete surfacea, such a~ 100r~ and the like. The compositions are part~cularly preferred for pol-iqhing floors and plastic tiles, such as linoleum, asphalt vinyl and vinyl-as~esto~. :
I~ generalO the ~ngrea~ents may be admixed $n the order de~ired. ~here a wax is employed ln the coating compos~tions, it 1~ usually added to the composition in the form o~ an emulsion.
Typical wax emulsion~ contain approximately 20 to 40% hy w~ight sol~ d and are formed by di~perslng the wax i~ water by means of a suitable an~onic or d~spersin~ agent. s~itabl~ agent3 ~ncluae sodlu~ ~alts of hlgher fatty acid ~ulfate~, the higher fatty acid 8alt8 ~ ~thylene oxide modified alkyl phenol~ and other con---- r:
.
' t ,':, ,;'" --' ~a8~L88 ventional dispersing agents. Particularly useful dispersing agents include amine salts of soap, such as ethanolamine or - morpholine oleate or stearate.
. .
The coating compositions can be applied to numerous substrates as set forth hereinbefore by various methods including application with a rag, mop, brush, non-woven cloth and by spraying and/or dipping.
The following examples are provided to further illustrate the present invention and are not limitive of '~
scope.
,, :
:
" EXAMPLE I
S~ To demonstrate the effectiveness of the present ~ invention, several self-stripping coating compositions .
~-, were prepared. Unless otherwise stated, the weights of .,.~, .
~ the ingredients are in parts by weight.
. .
PARTS/
COMPONENT PARTS NON-VOLATILE
~ Styrene Acrylic Acid Resin : Solution (20~) 58.800 11 760 20 Tributoxyethyl Phosphate0.600 0 600 Oleic Acid 0.600 0.600 Octylphenoxy Polyethoxy Ethanol (70%) 0.686 0.480 Polyethylene Wax Emulsion (25%) 1.680 0.420 Polypropylene Wax Emulsion (25~) 0.560 0.140 ~ Pentel ~ 3611 Fluorochemical 0.020 ----~ Concentrated Ammonium Hydroxide 1.400 ---Water 35.454 ---Perfume 0.100 ---Dye at 1% _0.100 ---; 100.000 14.000 The pH of the composition was 9.6. The bulk of - the non-volatiles were derived from the styrene-acrylic acid resin solution with the other percentage of non-volatiles being 19.05% of the resin non-volatiles (non-resin non-~olatiles). The resin was a low molecular weight acidic copolymer with a monomer distribution of 68%
48~
styrene and 32% acrylic acid, based on the weight ofcopolymer. The resin solids have an acid number of 180 to 190. The resin solution also contained minor quantities of a sequestering agent and hyclrogen perioxide for cosmetic purposes.
.
. .
, 1 0 .' - ~ ' `.' ", '"''.
. ' ' :
;.' ' ' . ' ', ''" ~
-17a-: :, . . . . .
.
8~
resin ~olutlon addlt~on~lly contalned 5~ o~ diet~ylen~ glycol ~onoethyl ether~
The composit~on had ~xcellent storag~ stab~ llty. ~he ~ composition wa~ applied to ~ vlnyl 100r by con~entlon~l mean3 and ;:
allowed to dry, The dried pol~h ~wa~ ~cuffed and scra~ched. A
- ~econd coat of pol~h wa9 applled to the dried coa~ and th~ 3cuff~
: ~nd ~cratche~ were readlly re~oved. The above compo~ltlon pr~vided . .
. a non-yellow~ng floor pollsh w~th ,exc~llent wa~er spotting re~
- ~ance.
.:
.'.- . .
. . EX~LE I~
A ~loor coatlng composit1on having the followlng formu-lation was prepared:
:: CO~O~ENT PAR~S BY WEIGHT
, ,; Polymer ~ 34.7% solid~* ~9.865 Water S7.816 .. ~mmonium ~Iydrox~de ` 3~500 Carb~tol fi~ ` 5 1% solution o~ Pentel~3611 Yluorochemical 0.500 ~rito ~ X-405 (7~% solids) 0.~23 ~ributoxyethyl Pho~phatef~ 0.576 . 25% solids emulsion of A ~ 392 Polyethylene Wax 1.~20 .
p~ ~ 9.70 ~on-volatiles ~ 12.0%
Non-re~in ~on-volatiles ~ 15~8%
* The ~ono~er compo~itlon of the polymer wa~ as follows:
Methylmethacrylate 46.~%
Butyl Acrylate 30.0 ~ethacrylic ~c~d 23.8%
Ac~d number o 155 and the molecular weights a~ detexmined by G.P.C. were .~ ~ 12~100 . ~Sw ~ 32tlO0 When thi~ formulation was ut~lized to coat a floor, the . ~ame was completely self-~tripplng and had good glos~ and leveling characteristlc~.
.
..
EXA~LE III
A ~tr~ppablQ floor ~oatln~ compo~ition having the ~ollowing foEmulatlon wa~ prepare~:
f~ ~
-- - r lr~4~
COMPONENT PARTS BY WEIGHT
~ Water 51.666 :~ Concentrated Ammonium Hydroxide 1.221 . Carbitol 4.568 Pentel ~ 3611 Fluorochemical (25%) 0.020 Triton ~X-405 t70%) 0.698 ~ Oleic Acid 0.610 - Styrene Acrylic Acid Solution (25.3%)* 36.623 Tributoxyethyl Phosphate 0.610 - AC ~ 392 Wax Emulsion (25%) 1.953 : Poly EM ~ - 20 Wax Emulsion (40%) 1.831 Perfume 0.100 ~- Dye (1%) 0.100 ., 100 . 000 ,;
. Non-volatile = 12%
Non-resin non-volatile = 28.3%
pH = 9.6 .
* The resin is 67.5% S and 32.5% AA and has :, an acid number of 180 to 190. The Mn is 3,600 ~ to 4,000 and Mrw is 7,000 to 8,000.
: When utili~ed as a floor coating composition, this formulation had excellent gloss and leveling character-istics and was self-stripping, relatively water-insensitive, and was reasonably durable in use.
': :
. EXAMPLE IV
A floor coating composition having the following . 20 formulation was prepared:
COMPONENT PARTS BY WEIGHT
Water 33.356 Ethylene Glycol 5.000 ~; Triton ~ X-405 (70%) 0.800 :: SMA ~ Resin Solution* (20%)51.450 Polymer Emulsion (35%)** 5.000 Tributoxyethyl Phosphate 0.840 :: AC ~ 392 Polyethylene Wax Emulsion (25%) 2.154 Concentrated Ammonium Hydroxide 1.200 Dye (1%) 0.100 : Perfume 0.100 ,, 100. 000 ~' pH = 9.75 Non-volatile = 14.0%
Non-resin non-volatile = 36.05%
: * Resin solution is 20% solution of SMA~17352 .- from ARCO ~. Resin has acid number of 260 to 280. The solution contains fatty acid and fluorochemical.
-~ ** The polymer is a 35% solids emulsion of a polymer with the following monomer distribution:
3~% methyl methacrylate ~- 52% 2-ethylhexylacrylate 9% methacrylic acid The molecular weight of the polymer is in excess of 200,000.
. ~, - This formulation, when applied to the floor as a floor wa~ or coating composition, had excellent initial le~eling and gloss as well as good gloss and leveling characteristics subsequent to the utilization of the same as a self-stripping cleaner. Furthermore, the sensitivity ;~ 10 to water and the durability to traffic were judged as good.
!
EXAMPLE V
A still further floor coating composition was prepared ha~ing the formulation as follows:
_l~PONENT PARTS BY WEIGHT
Water 33.488 Ethylen~ Glycol 3.870 Triton ~Y X-405 (70~) 0.800 Fluo~ochemical ~C ~Y - 420 (1%) 0.500 SMA ~Resin Solution (20%)*46.200 Polymer Solution ** 10.048 Tributoxyethyl Phosphate 0.840 Tall Oil Fa~ty Acid 0.700 Anionic AC ~392 Polyethylene Wax Emulsion (25%) 2.154 Concentrated Ammonium Hydroxide 1.200 Dye (1%) 0.100 Perfume 0.100 100.000 pH = 9.75 Non-volatile = 14%
Non-resin non-volatile = 51.52%
,~
* A 20%~solids solution of SMAW 17352 (supplied by ARCd~ ~ in H20 and NH40H. Resin has acid number of 260 to 280.
** A 20.9% solids solution of polymer in sol~ent, NH4OH and H2O. The polymer has a molecular weight of greater than 200,000 and the following monomer distribution:
42% methyl methacrylate 50% 2-ethylhexyLacrylate 8% methacrylic acid This formulation, like the formulation from Example I~, utilized ethylene glycol in place o~ the ,~
polyether utilized hereto:Eore. The floor coating composi- -tion was quite satisfactory as regards self-stripping . :, , properties and had good gloss and leveling characteristics as well as good durability to traffic and moderate water - resistance.
~, .
EX~MPLE ~I
A still further floor coating composition in accordance with the present invention was prepared having the formulation as follows:
COMPONENTS PARTS BY WEIGHT , , Water 52.272 - Ammonium Hydroxide 1.200 ~, Carbitol 3.783 Pent~l ~)3611 Fluorochemical(25%) 0.020 `~ Triton (~X-405 (70%) `0.686 Oleic Acid 0 600 Resin Solution* 36 919 , Tributoxyethyl Phosphate 0.600 -- AC ~) - 392 Wax Emulsion ~25%) 1.920 Poly EM ~) 20 Wax Emulsion (40%) 1.800 Perfume 0.100 Dye (1%) 0.100 100 . 000 , , pH = 9.6 -' Non-volatile = 12.0%
Non-resin non-v-~olatile = 31.59%
* Resin solution is 24.7% non-volatile and contains a solution prepared copolymer with the follo~ing monomer composition: 59% S, 10% BuA, 31% A~. Mw c 10,000.
;; This formulation performed quite adequately ., as regard to coating characteristics and especially self-stripping capacity, high gloss and leveling character-,, .
istics. The durability and resistance to water spotting ~, were good.
i~, EX~MPLE VII
I A still :Eurther composition in accordance with i, the present invention for use as a floor coating composition was prepared having the following formulation:
.. . .
~ --21--, , ~ . , .
~ . ,. . : . " . . . :
8~8~
~.`
` _OMPONENT PARTS BY WEIGHT
Water 39.060 Ammonium Hydroxide 1.396 Caxbitol 4.985 Pentel ~ 3611 Fluorochemical (25%) 0.020 Triton ~X-405 (70%) 0.800 - SMA ~ Resin Solution *48.055 Tr~butoxyethyl Phosphate0.598 AC~ - 392 Wax Emulsion (25%)4.786 Dye (1%) 0.200 Perfume 0 100 .~ 100 000 pH = 9.65 Non-volatile = 12%
Non-resin non-volatile = 24.85%
* SMA~ resin solutio~-is 20% non-volatile - and ~s made from SMA 17352A supplied by ARCO~Y. It has an acid number of 260 to 280.
- When coated on tile floors as a floor polish composition, the above composition showed excellent self-- stripping capacity, good gloss and leveling characteristics, as well as reasonable resistance to water spotting and adequate durability to traffic.
.::
EXAMPLE VII
A formulation having the concentrate composition as follows was prepared:
COMPONENT PARTS BY WEIGHT
~ater 53.731 r Ammonium Hydroxide 1.400 Carbitol 0 882 - Pentel ~ 3611 Fluorochemical (25%~ 0 020 ` Triton ~ X-405 (70%) 0.686 Oleic Acid 0.600 - Styrene Acrylic Acid Resin (20%)* 28.800 Polymer Emulsion ** 9.361 - Tributoxyethyl Phosphate 0.600 Poly EM OE~20 Wax Emulsion (40%~ 1.800 AC @~- 392 Polyethylene Wax Emulsion 1.920 - Dye ~1%) 0.100 Perfume 0.100 100 . 000 pH = 9.6 Non-volatile = 12%
Non-resin non-volatile = 120.93%
* The resin has an acid number of 180 to 190 and is 67.5% S and 32.5% AA.
': . . ' . ' . ' . ' . ' . ' ' ' i ' ' ' " ~ . ' ' . .. ' ' .. ** The polymer~emu-l~sion is 35%.non-volatile -~- a~d has the ~qllo~n~ monomer distr~bution: lU parts st~rene . 50 parts ~ethylmethacrylate 30 parts Dut~l acrylate .- 10.parts.methacrylic acid .
The molecular weig~ts of the polymer are as follows:
Mn = 4,200 Mw = 9,000 .
When the above formulat:ion was utilized as a floor - coating composition in accordance with the present invention, the same had excellent self-stripping capacity, as well as .
: good gloss, durability, and leveling characteristics. Also, the resistance to water spotting was adequate.
. EXAMP E -IX
. A composition in accordance with the present :. , .
:~ invention which is designed to be diluted with water before use : .. to approximately 2-20% solids was prepared having the following . ~ composition: `
.. . .
COMPONENT PARTS:BY WEIGHT
. Wa~er 32.03 Trisodium NTA 1.50 :"`
: Propylene Glycol 17~00 Pentel ~ 3611 Fluorochemical (1%) 0.50 .: Concentrated~Ammonium Hydroxi~e . 15.00 Water SolubIe Blue Dye at 1% 0.10 .20 Tributoxyethyl Phosph~te 1.59 ; Styrene~Acrylic Acid Resin Flakes* , 33.98`
~ Triton ~y X-405 1.90 :: Tall Oil Fatty Acid 1.59 ;~ pH ~ 9.6 Non-volatile = 40%
Non-resin non-volatile = 17.71%
* The resin is 67.5% styrene and 32.5%
; acrylic acid. It has an acid number of 1~0 to 190. Mn = 3,600 to 4,000 and Mw = 7,000 to 8,000.
;, . When the above formulation was diluted with water to ~, .
;. - 4~ soli~s, t~e d~luted composition had excellent self-stripping properties, ex~ellent dura~tlity, excellent gloss and leveling characteristics. Also, the re$istance to water spotting was good.
- -23- `
, . ,~
.
8~
When the above compoSition was diluted to 20% solids, -~` the results upon coating ~ere al~o ~ui~te good with the 20%
solids compo6ition having good ~elf stripp~ng action, high gloss and durability, as well as leveling characteristics.
Also, when the above formulation was prepared as a
2% solids dilution, the composition performed adequately.
Although the gloss was somewhat reduced, the composition was self-stripping and was reasonably level.
EXAMPLE X
A still further bucket-dilutable formulation having the composition as follows was prepared:
COMPONENT PARTS BY WEIG~T
Water ~ 221 562 ~ Oleic Acid 2 11 `~ Pentel ~ 3611 Fluorochemical (25%)0 02 `~ Tributoxyethyl Phosphate 2.11 - Tetrasodium EDTA 0.35 Isopropyl Alcohol 17 81 Styrene Acrylic Acid Resin Flakes*42 95 Concentrated Ammonium Hydroxide10.53 ' ~ . 100.00 pH = 9.6 Non-volatile = 47%
` Non-resin non-volatile = 9.42~
* The resin is 67.5~ styrene and 32.5~ acrylic acid. The acid number ls 180, and the Mn =
~ 3,600 to 4,000 and Mw = 7,000 to 8,000.
- When the above formulation was diluted within the range of from 4~ to 18% sollds, the same produced good gloss and leveling ~h~a~eristics on the floor and was completely self-strippable. -Alternatively, the above composition was applied to the substrate full strength and diluted on the floor with a .,.1 .
wet sponge mop. When applled in *his manner, the composition also had excellent gloss and leveling characteristics and ~.1 ` 30 was-self-stripping.
; -2~-8~8 EXAMPLE XI AWD COMPARATIVE EXAMPLES I & II
. In order to show the criticality of the acid numbers :.
: and molecular weight ranges in the composition of the present i ~
; invention, the following formulatlons, which are identical except for the polymer used, were prepared to give a product having a . pH = 9.6, a non-volatiles lével of 12.0% and a non-resin non-volatile of 15.74~. Each polymer was formed from varying amounts o~ I~MA (methyl methacrylate), BA (butyl acrylate)la~d MAA
(methacrylic acid).
. 10 COMPARATIVE COMPARATIVE EXAMPLE
COM~NENT EXAMPLE I EX~MPLE II XI
i . ;= . .__ _ Water 47.620 48.306 47.317 Carbitol 5.000 5.000 5.000 : Amm~:ium hydroxide 2.600 1.800 3.000 FC ~- 420 fluorochemical(l~) 0.500 0.500 0.500 - Triton ~ X-405 (70~)0.823 0.823 0.823 Polymer A~ (25.30%) See 40.961 -~
Polymer B ~(25.23~) Table ------ 41.075 ------Polymer C- (25.37~ I ------ --~--- 40.864 ~ . Tritonloxyethyl phosphate 0.576 0.576 0.576 AC ~ -392 polyethylene was emulsion (25%) 1.920 1.920 1.920 .00'~ 100'.0-00 100.000 Viscosity 28.5 cps 7.0 cps 8.5 cps TABLE I
, 20 Composition Acid Number : :
of Pol_mer of Polymer Mw Mn Polymer A 50 MMA I4198,500 21,780 30 BuA
Polymer B 55 MMA 11040,000 11,420 30 BuA ^
Polymer C 44 MMA 18318,400 6,140 30 BuA
The Mn and Mw were determined by gel permeation chromatography and the acid nu~bers were obPained by adjusting the levels-o-E methyl methacr~late and methacrylic aaid. In Comparative Example It the Mw is above the range of the present .~.
invention althoug~ the acid number is within the critical range. Compara~ive Example II has a molecular weight within .
:.' . :'' . ., : . . . .
the range of the present invention, but the acid number is too low. Example XI is with;~n the ~ope of the present invention.
-~ The performance of the ~a~ove products was tested on ~loors using sponge mops and normal application techniques. The high molecular weight and relatively high acid number of Compara-tive Example I caused its viscosity to be higher than the vis-` cosity of Comparative Example II and Example XI. ~he products were allowed to cure under ambient conditions for one week and ` then the dry films were recoated with the respective products.
Comparative Example I became excessively viscous as it dissolved some of the previous film and leveled poorly, exhibiting marks due to the application strokes. In addition, etching occurred . :
where the product was puddled prior to spreading out over the floor. Since this redissolving of the prevlous coat was so slow, only partial removal occurred, and the final appearance was undesirable as a floor polish. It contained streaks due to the poor leveling, puddle marks due to the etching and uneven gloss.
Although Comparative Example II did not exhibit ~ excessive viscosity when reappliéd, it did etch into thé dry film where the liquid product was initially puddled. In this case also, the redissolving of the previous coat was too slow and extensive removal occurred only where the puddle was situated.
... .
The final appearance was undesirable because of this puddle mark and the uneven gloss. Example XI, on the other hand, was :;
able to rapidly redissolve the previous film wherever the fresh product came into contact with it, and the old coat was .
completely stripped within a very short period of time. The final film was uniformly glGs~y and it was not posslble to de'tect where the product ha~ been puddled.
~` .. ' . .
.
.: . . . :
~04~3,88 EXAMPLE XII
. . ~ . , A fl~or finish composltion having the followlng formula was prepared:
.
:. COMPONENT PARTS BY ~IGIiT
: Polymer emulsion C~ 35% solids~ 29.609 ` Water 5B.572 Concentrated Ammonium Hydroxide 3.000 Carbltol 5O000 -:~ 1% solution of Pentel~ 611 Fluorochemical 0.500 ;: Triton~ X-405 (70%) 0.8~3 . Tributoxyethyl Phosphate 0~576 AC R-392 Polyethylene Wax Emulsion ~25%)1.920 , 100.000 p~ - 9.7 Non-volatile~ = 12.0%
Non-re~in non-volatiles - 15.
..
* Monomer composition of'pol~mer:
Methyl Methacrylate46.2%
Butyl Acytate 30.0%
: ¦ ~ethacrylic Acid 23~8 Acid Numbe~ = 155 . M~ ~ 13,500 1~ = 39,400 , The composition was self-stripping and performed sati~-factorily, however9 the glosq and level~ng properties were not as .. ,~ .
good as the lower molecular weight formula (Example II~ .
'' : EXP*~LE XIII
. :
A floor finish composition having the following compo-sition was prepared:
~- COMPONENT PARTS BY WEIG~T
~ 20% polymer solution* 50.470 : ~leic Rcid 0 . 360 : Perfume 0.150 :. Dye (1%) 0~100 Chelating agent ~ 0.100 ; 1~ solu~ion of Pen~:e~3611 Fluorochemical 0.500 Polypropylene Glycol (.1w=400) 1.000 ~ Ammon~a 1.733 Water f~ 43.373 25% AC~ 92 Polyethylene Wax Emulsion1.440 27.2% E-43 Polypropylene Emuls~on 0.441 30~ Hydrogen Peroxide 0.333 10~ u 000 pH =5 9O7 . Non-volatiles ~ 1~0%
Non-resin non-volatile~ - 19.0%
~.
-2~-., ,, ~ ;
L8i~ ' *The monomer composition of the polymer ~as as follows~;
45% ~-Met~ styrene ; 30% Eth~l Acr~late 25% Acrylic Acid The Mn of the polymer was 3,120, the Mw ~' was 4~800r and it had an acid number of 155.
This formulation was self-stripping and had good gloss and leveling.
., .
Other modifications may be made in the compositions as will be obvious to those skilled in the art. The invention is not to be limited except as set forth~in the following claims.
. ~:
. .
, ., '~' .
' ": :
.. . ..
. , , ... . . . . . . ..
Although the gloss was somewhat reduced, the composition was self-stripping and was reasonably level.
EXAMPLE X
A still further bucket-dilutable formulation having the composition as follows was prepared:
COMPONENT PARTS BY WEIG~T
Water ~ 221 562 ~ Oleic Acid 2 11 `~ Pentel ~ 3611 Fluorochemical (25%)0 02 `~ Tributoxyethyl Phosphate 2.11 - Tetrasodium EDTA 0.35 Isopropyl Alcohol 17 81 Styrene Acrylic Acid Resin Flakes*42 95 Concentrated Ammonium Hydroxide10.53 ' ~ . 100.00 pH = 9.6 Non-volatile = 47%
` Non-resin non-volatile = 9.42~
* The resin is 67.5~ styrene and 32.5~ acrylic acid. The acid number ls 180, and the Mn =
~ 3,600 to 4,000 and Mw = 7,000 to 8,000.
- When the above formulation was diluted within the range of from 4~ to 18% sollds, the same produced good gloss and leveling ~h~a~eristics on the floor and was completely self-strippable. -Alternatively, the above composition was applied to the substrate full strength and diluted on the floor with a .,.1 .
wet sponge mop. When applled in *his manner, the composition also had excellent gloss and leveling characteristics and ~.1 ` 30 was-self-stripping.
; -2~-8~8 EXAMPLE XI AWD COMPARATIVE EXAMPLES I & II
. In order to show the criticality of the acid numbers :.
: and molecular weight ranges in the composition of the present i ~
; invention, the following formulatlons, which are identical except for the polymer used, were prepared to give a product having a . pH = 9.6, a non-volatiles lével of 12.0% and a non-resin non-volatile of 15.74~. Each polymer was formed from varying amounts o~ I~MA (methyl methacrylate), BA (butyl acrylate)la~d MAA
(methacrylic acid).
. 10 COMPARATIVE COMPARATIVE EXAMPLE
COM~NENT EXAMPLE I EX~MPLE II XI
i . ;= . .__ _ Water 47.620 48.306 47.317 Carbitol 5.000 5.000 5.000 : Amm~:ium hydroxide 2.600 1.800 3.000 FC ~- 420 fluorochemical(l~) 0.500 0.500 0.500 - Triton ~ X-405 (70~)0.823 0.823 0.823 Polymer A~ (25.30%) See 40.961 -~
Polymer B ~(25.23~) Table ------ 41.075 ------Polymer C- (25.37~ I ------ --~--- 40.864 ~ . Tritonloxyethyl phosphate 0.576 0.576 0.576 AC ~ -392 polyethylene was emulsion (25%) 1.920 1.920 1.920 .00'~ 100'.0-00 100.000 Viscosity 28.5 cps 7.0 cps 8.5 cps TABLE I
, 20 Composition Acid Number : :
of Pol_mer of Polymer Mw Mn Polymer A 50 MMA I4198,500 21,780 30 BuA
Polymer B 55 MMA 11040,000 11,420 30 BuA ^
Polymer C 44 MMA 18318,400 6,140 30 BuA
The Mn and Mw were determined by gel permeation chromatography and the acid nu~bers were obPained by adjusting the levels-o-E methyl methacr~late and methacrylic aaid. In Comparative Example It the Mw is above the range of the present .~.
invention althoug~ the acid number is within the critical range. Compara~ive Example II has a molecular weight within .
:.' . :'' . ., : . . . .
the range of the present invention, but the acid number is too low. Example XI is with;~n the ~ope of the present invention.
-~ The performance of the ~a~ove products was tested on ~loors using sponge mops and normal application techniques. The high molecular weight and relatively high acid number of Compara-tive Example I caused its viscosity to be higher than the vis-` cosity of Comparative Example II and Example XI. ~he products were allowed to cure under ambient conditions for one week and ` then the dry films were recoated with the respective products.
Comparative Example I became excessively viscous as it dissolved some of the previous film and leveled poorly, exhibiting marks due to the application strokes. In addition, etching occurred . :
where the product was puddled prior to spreading out over the floor. Since this redissolving of the prevlous coat was so slow, only partial removal occurred, and the final appearance was undesirable as a floor polish. It contained streaks due to the poor leveling, puddle marks due to the etching and uneven gloss.
Although Comparative Example II did not exhibit ~ excessive viscosity when reappliéd, it did etch into thé dry film where the liquid product was initially puddled. In this case also, the redissolving of the previous coat was too slow and extensive removal occurred only where the puddle was situated.
... .
The final appearance was undesirable because of this puddle mark and the uneven gloss. Example XI, on the other hand, was :;
able to rapidly redissolve the previous film wherever the fresh product came into contact with it, and the old coat was .
completely stripped within a very short period of time. The final film was uniformly glGs~y and it was not posslble to de'tect where the product ha~ been puddled.
~` .. ' . .
.
.: . . . :
~04~3,88 EXAMPLE XII
. . ~ . , A fl~or finish composltion having the followlng formula was prepared:
.
:. COMPONENT PARTS BY ~IGIiT
: Polymer emulsion C~ 35% solids~ 29.609 ` Water 5B.572 Concentrated Ammonium Hydroxide 3.000 Carbltol 5O000 -:~ 1% solution of Pentel~ 611 Fluorochemical 0.500 ;: Triton~ X-405 (70%) 0.8~3 . Tributoxyethyl Phosphate 0~576 AC R-392 Polyethylene Wax Emulsion ~25%)1.920 , 100.000 p~ - 9.7 Non-volatile~ = 12.0%
Non-re~in non-volatiles - 15.
..
* Monomer composition of'pol~mer:
Methyl Methacrylate46.2%
Butyl Acytate 30.0%
: ¦ ~ethacrylic Acid 23~8 Acid Numbe~ = 155 . M~ ~ 13,500 1~ = 39,400 , The composition was self-stripping and performed sati~-factorily, however9 the glosq and level~ng properties were not as .. ,~ .
good as the lower molecular weight formula (Example II~ .
'' : EXP*~LE XIII
. :
A floor finish composition having the following compo-sition was prepared:
~- COMPONENT PARTS BY WEIG~T
~ 20% polymer solution* 50.470 : ~leic Rcid 0 . 360 : Perfume 0.150 :. Dye (1%) 0~100 Chelating agent ~ 0.100 ; 1~ solu~ion of Pen~:e~3611 Fluorochemical 0.500 Polypropylene Glycol (.1w=400) 1.000 ~ Ammon~a 1.733 Water f~ 43.373 25% AC~ 92 Polyethylene Wax Emulsion1.440 27.2% E-43 Polypropylene Emuls~on 0.441 30~ Hydrogen Peroxide 0.333 10~ u 000 pH =5 9O7 . Non-volatiles ~ 1~0%
Non-resin non-volatile~ - 19.0%
~.
-2~-., ,, ~ ;
L8i~ ' *The monomer composition of the polymer ~as as follows~;
45% ~-Met~ styrene ; 30% Eth~l Acr~late 25% Acrylic Acid The Mn of the polymer was 3,120, the Mw ~' was 4~800r and it had an acid number of 155.
This formulation was self-stripping and had good gloss and leveling.
., .
Other modifications may be made in the compositions as will be obvious to those skilled in the art. The invention is not to be limited except as set forth~in the following claims.
. ~:
. .
, ., '~' .
' ": :
.. . ..
. , , ... . . . . . . ..
Claims (16)
1. In a stable coating composition adapted to simul-taneously disperse a previously deposited dried coating composition and replace the dried composition with a fresh coat comprising:
50-96% water, 0-10% plasticizer, 0-5% leveling agent, 0-10% organic solvent, 0-5% surfactant, 0-15% wax, 0-10% film-modifying polymer and 3-18% polymeric coating agent; with the proviso that the total non-volatiles of the composition is in the range of from 4-20% by weight and the combined non-volatiles of the leveling agent.
solvent, plasticizer, surfactant, wax and film-modifying polymer are equal to or greater than 9% of the non-volatiles of the polymeric coating agent; the improvement which comprises using as the polymeric coating agent a solution of an alkali-soluble resin having a weight average molecular weight from about 500 to 40,000 and an acid number from about 120 to 550, said resin being an addition resin formed from (a) at least 1 ethylenically unsaturated ligand-free monomer and (b) at least 1 ethylenically unsaturated monomer having at least 1 carboxyl group, wherein said resins con-tain from about 40-85% by weight of monomer (a) and from 60-15%
by weight monomer (b), adding aqueous ammonia to said composition in an amount sufficient to provide a pH of no less than 9.0, and said composition being substantially free of complex salts of cross-linking metals.
50-96% water, 0-10% plasticizer, 0-5% leveling agent, 0-10% organic solvent, 0-5% surfactant, 0-15% wax, 0-10% film-modifying polymer and 3-18% polymeric coating agent; with the proviso that the total non-volatiles of the composition is in the range of from 4-20% by weight and the combined non-volatiles of the leveling agent.
solvent, plasticizer, surfactant, wax and film-modifying polymer are equal to or greater than 9% of the non-volatiles of the polymeric coating agent; the improvement which comprises using as the polymeric coating agent a solution of an alkali-soluble resin having a weight average molecular weight from about 500 to 40,000 and an acid number from about 120 to 550, said resin being an addition resin formed from (a) at least 1 ethylenically unsaturated ligand-free monomer and (b) at least 1 ethylenically unsaturated monomer having at least 1 carboxyl group, wherein said resins con-tain from about 40-85% by weight of monomer (a) and from 60-15%
by weight monomer (b), adding aqueous ammonia to said composition in an amount sufficient to provide a pH of no less than 9.0, and said composition being substantially free of complex salts of cross-linking metals.
2. The composition of claim 1 wherein said ligand-free monomer is selected from the group consisting of vinyl toluene, methyl methacrylate, butyl methacrylate, acrylonitrile, vinyl acetate, styrene, .alpha.-methyl styrene, butyl acrylate, ethyl acrylate, 2-ethylhexylacrylate and mixtures thereof.
3. The composition of claim 1 wherein the ethylenically unsaturated monomer having at least 1 carboxyl group is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid and itaconic acid.
4. The composition of claim 1 wherein the acid number of the resin is from about 150 to 300.
5. The composition of claim 4 wherein the acid number is from about 150 to 250.
6. The composition of claim 1 wherein the molecular weight of the resin is from about 500 to 30,000.
7. The composition of claim 1 wherein the pH is at least 9.5.
8. The composition of claim 6 wherein the molecular weight of the resin is from about 500 to 10,000.
9. The composition of claim 2 wherein the ethylenically unsaturated monomer having at least 1 carboxyl group is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid and itaconic acid.
10. The composition of claim 1 wherein said resin con-tains from about 40 to 75% monomer (a) and 60 to 25% monomer (b).
11. The composition of claim 3 wherein said resin con-tains from about 40 t 75% monomer (a) and 60 to 25% monomer (b).
12. The composition of claim 3 wherein the molecular weight of the resin is from about 500 to 30,000.
13. The composition of claim 12 wherein the molecular weight of the resin is from about 500 to 10,000.
14. The composition of claim 13 wherein the resin is about 45% .alpha.-methyl styrene, about 30% ethyl acrylate and about 25% acrylic acid.
15. The composition of claim 13 wherein the resin is about 68% styrene and about 32% acrylic acid.
16. The composition of claim 13 wherein the resin is partially esterified styrene-maleic anhydride resin having an acid number of about 200 and a molecular weight of about 1400.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/480,981 US4013607A (en) | 1974-06-19 | 1974-06-19 | Self-stripping coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048188A true CA1048188A (en) | 1979-02-06 |
Family
ID=23910102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,046A Expired CA1048188A (en) | 1974-06-19 | 1975-06-11 | Self-stripping coating composition |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4013607A (en) |
| CA (1) | CA1048188A (en) |
| DE (1) | DE2527515C2 (en) |
| FR (1) | FR2332312A1 (en) |
| GB (1) | GB1515943A (en) |
| IT (1) | IT1040626B (en) |
| NL (1) | NL182326C (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168255A (en) * | 1974-05-06 | 1979-09-18 | Rohm And Haas Company | Oligomeric aqueous finishes |
| US4230605A (en) * | 1978-12-13 | 1980-10-28 | Armstrong Cork Company | Cleaning composition for no-wax vinyl composition floor covering |
| US4317755A (en) * | 1980-06-11 | 1982-03-02 | S. C. Johnson & Son, Inc. | Self-polishing sealing composition |
| US4299749A (en) * | 1980-06-30 | 1981-11-10 | Sterling Drug Inc. | Floor coating composition |
| US4414370A (en) * | 1981-01-09 | 1983-11-08 | S. C. Johnson & Son, Inc. | Process for continuous bulk copolymerization of vinyl monomers |
| US4414360A (en) * | 1981-04-13 | 1983-11-08 | Purex Corporation | Spray buff reactant and application thereof |
| US4529787A (en) * | 1982-06-15 | 1985-07-16 | S. C. Johnson & Son, Inc. | Bulk polymerization process for preparing high solids and uniform copolymers |
| DE3323939A1 (en) * | 1983-07-02 | 1985-01-03 | Henkel KGaA, 4000 Düsseldorf | LIQUID SHOE AND LEATHER CARE |
| US4618514A (en) * | 1985-12-20 | 1986-10-21 | Rca Corporation | Alignment layer for liquid crystal display |
| EP0239084A3 (en) * | 1986-03-26 | 1989-03-29 | S.C. Johnson & Son, Inc. | Non-homogenized multi-surface polish compositions |
| US4869934A (en) * | 1988-09-16 | 1989-09-26 | Sterling Drug Inc. | Floor polishing and coating composition |
| US4942193A (en) * | 1988-10-11 | 1990-07-17 | Ppg Industries, Inc. | Temporary protective coating compositions |
| US5081174A (en) * | 1988-10-11 | 1992-01-14 | Ppg Industries, Inc. | Protective coating composition |
| US5639814A (en) * | 1988-10-11 | 1997-06-17 | Ppg Industries, Inc. | Temporary protective coating compositions capable of low temperature drying |
| US5229450A (en) * | 1988-10-11 | 1993-07-20 | Ppg Industries, Inc. | Temporary protective coating compositions |
| FR2663940B1 (en) * | 1990-07-02 | 1994-04-08 | Rhone Poulenc Chimie | GRAFT POLYSACCHARIDES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS SEQUESTRATION AGENTS. |
| FR2663948B1 (en) * | 1990-07-02 | 1994-06-03 | Rhone Poulenc Chimie | DETERGENT COMPOSITION CONTAINING A BIODEGRADABLE GRAFT POLYSACCHARIDE. |
| US5147924A (en) * | 1991-02-20 | 1992-09-15 | Air Products And Chemicals, Inc. | Selectively soluble, protective coating compositions derived from vinyl acetate/monoalkyl maleate copolymers |
| JP3084328B2 (en) * | 1991-12-26 | 2000-09-04 | 株式会社サクラクレパス | Water-based water-based ink composition |
| DE4243475A1 (en) * | 1992-12-22 | 1994-06-23 | Henkel Ecolab Gmbh & Co Ohg | Neutral wiping agent (I) |
| CA2159611C (en) * | 1993-03-30 | 2005-01-11 | Francis J. Koreltz | Improved floor stripping composition and method |
| KR960701186A (en) * | 1993-03-30 | 1996-02-24 | 테릴 켄트 퀼리 | MULTI-SURFACE CLEANING COMPOSITIONS AND METHOD OF USE |
| CN1082997C (en) * | 1993-03-30 | 2002-04-17 | 美国3M公司 | Cleaning compositions and methods of use |
| US5491190A (en) * | 1993-07-22 | 1996-02-13 | S. C. Johnson & Son, Inc. | Repulpable hot melt polymer/fatty acid compositions for fibrous products |
| EP0746423A4 (en) * | 1993-07-22 | 1998-03-18 | Johnson & Son Inc S C | Repulpable hot melt polymer/wax compositions for fibrous products |
| US5604192A (en) * | 1994-06-22 | 1997-02-18 | The Procter & Gamble Company | Hard surface detergent compositions |
| ES2153900T3 (en) * | 1994-07-21 | 2001-03-16 | Minnesota Mining & Mfg | CONCENTRATED CLEANING COMPOSITIONS ABLE TO INCREASE VISCOSITY WITH DISSOLUTION. |
| US5773077A (en) * | 1995-10-10 | 1998-06-30 | Ellay, Inc. | Abrasion-protective convertible window |
| DE69629101T2 (en) * | 1996-02-13 | 2004-02-12 | JohnsonDiversey, Inc., Sturtevant | Method and device for surface treatment |
| DE69637356T2 (en) | 1996-11-01 | 2008-10-30 | Laboratoires Choisy Ltee, Louisville | COATING OR SEALING COMPOSITION |
| US5922665A (en) * | 1997-05-28 | 1999-07-13 | Minnesota Mining And Manufacturing Company | Aqueous cleaning composition including a nonionic surfactant and a very slightly water-soluble organic solvent suitable for hydrophobic soil removal |
| JP3803819B2 (en) * | 2000-02-18 | 2006-08-02 | 日本パーカライジング株式会社 | Metal surface treatment agent and surface treated metal material treated with the same |
| DE10054284B4 (en) * | 2000-11-02 | 2010-04-08 | Manroland Ag | Process for the treatment of an erasable lithographic printing plate |
| US6849589B2 (en) | 2001-10-10 | 2005-02-01 | 3M Innovative Properties Company | Cleaning composition |
| KR100474582B1 (en) * | 2001-12-31 | 2005-03-08 | 주식회사 디피아이 | Ambient-curable Resin-fortified Emulsion And Method Of Preparing The Same |
| US20040225055A1 (en) * | 2003-05-06 | 2004-11-11 | Hans Haas | Cleaning process involving a dissolvable polymer coating |
| BRPI0504779A (en) * | 2004-11-08 | 2006-06-27 | Rohm & Haas | aqueous composition, method of preparation thereof, and aqueous formulation |
| US20070010607A1 (en) * | 2005-06-24 | 2007-01-11 | Smith Kim R | Surface treatment composition and method for treating a surface |
| US8013051B2 (en) * | 2007-02-09 | 2011-09-06 | Canon Kabushiki Kaisha | Liquid composition, image forming method, cartridge, recording unit and ink jet recording apparatus |
| US7918928B2 (en) | 2007-02-09 | 2011-04-05 | Canon Kabushiki Kaisha | Pigment ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus |
| CN101711275A (en) * | 2007-03-13 | 2010-05-19 | 伊莱门蒂斯专业有限公司 | biodegradable cleaning compositions |
| EP2976379A1 (en) | 2013-03-18 | 2016-01-27 | Basf Se | Method for producing polymer powders that can be easily redispersed in water |
| US9453139B2 (en) | 2013-08-20 | 2016-09-27 | Rohm And Haas Electronic Materials Llc | Hot melt compositions with improved etch resistance |
| EP3487895B1 (en) | 2016-07-20 | 2023-02-01 | Basf Se | Process for preparing an aqueous polymer dispersion having high chemical resistance |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA868423A (en) | 1971-04-13 | Molle John | Alkali soluble polymers and method of making same | |
| US3313755A (en) * | 1962-03-09 | 1967-04-11 | Knomark Inc | Aqueous polymer latices containing an emulsifier of a partial ester of a styrene-maleic acid anhydride copolymer |
| US3380944A (en) * | 1964-12-04 | 1968-04-30 | Hooker Chemical Corp | Ammonia soluble resin |
| US3320196A (en) * | 1965-08-13 | 1967-05-16 | Johnson & Son Inc S C | Coating composition comprising a terpolymer, an alkali soluble resin, and a zirconyl-fugitive ligand compound |
| US3598778A (en) * | 1967-01-19 | 1971-08-10 | Gulf Research Development Co | Ammonium hydroxide polymer solutions for floor polish compositions |
| US3711436A (en) * | 1971-03-02 | 1973-01-16 | Sinclair Koppers Co | Floor polish composition having improved initial water and detergent resistance |
| US3793275A (en) * | 1971-10-01 | 1974-02-19 | American Home Prod | Hard surface polishes |
-
1974
- 1974-06-19 US US05/480,981 patent/US4013607A/en not_active Expired - Lifetime
-
1975
- 1975-06-02 GB GB23838/75A patent/GB1515943A/en not_active Expired
- 1975-06-11 CA CA229,046A patent/CA1048188A/en not_active Expired
- 1975-06-13 NL NLAANVRAGE7507073,A patent/NL182326C/en not_active IP Right Cessation
- 1975-06-18 DE DE2527515A patent/DE2527515C2/en not_active Expired
- 1975-06-18 IT IT50108/75A patent/IT1040626B/en active
- 1975-06-18 FR FR7519113A patent/FR2332312A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL182326C (en) | 1988-02-16 |
| NL7507073A (en) | 1975-12-23 |
| GB1515943A (en) | 1978-06-28 |
| AU8193775A (en) | 1976-12-16 |
| US4013607A (en) | 1977-03-22 |
| DE2527515C2 (en) | 1986-12-04 |
| DE2527515A1 (en) | 1976-01-08 |
| IT1040626B (en) | 1979-12-20 |
| FR2332312B1 (en) | 1979-10-19 |
| FR2332312A1 (en) | 1977-06-17 |
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